An organic-inorganic hybrid molybdenum oxide nanosheet and its preparation method

Abstract

This invention proposes an organic-inorganic hybrid molybdenum oxide nanosheet and its preparation method, belonging to the technical field of novel functional nanomaterials, to solve the technical problem of large molybdenum oxide sheet size. The preparation method of this invention includes the following steps: adding molybdenum oxide and an organic modifier to a mixed solvent for mixing and reaction; removing the reaction solvent to obtain the organic-inorganic hybrid molybdenum oxide nanosheet; the mixed solvent includes water and ethanol. The preparation method of this invention is simple in process and equipment, uses inexpensive and readily available raw materials, has low cost and high yield, and is suitable for large-scale industrial production. The prepared organic-inorganic hybrid molybdenum oxide nanosheets exhibit good dispersion stability in lubricating fluids.

Description

Technical Field

[0001] This invention belongs to the technical field of novel functional nanomaterials, and particularly relates to an organic-inorganic hybrid molybdenum oxide nanosheet and its preparation method. Background Technology

[0002] Transition metal oxides have wide applications in energy storage, electronics, catalysis, and solid lubrication. Among transition metal oxides, molybdenum trioxide (MoO3) is a low-cost and widely used metal oxide with compact structure, high thermal stability, two-dimensional layered structure, and diverse morphologies, making it a promising high-performance lubricant additive. Molybdenum trioxide has at least four known crystal phases [orthorhombic phase (α-MoO3), monoclinic phase (β-MoO3), hexagonal phase (h-MoO3), and high-pressure monoclinic phase (MoO3-ii)]. Among them, α-MoO3 has been extensively studied due to its unique layered structure, which consists of a bilayer planar crystal of twisted MoO6 octahedrons bonded together in the direction perpendicular to

[010] by weak van der Waals forces. Currently, molybdenum oxide nanosheets can be synthesized by various methods, including hydrothermal synthesis (Solid State Ionics, 2018, 326: 1–4), chemical and physical vapor deposition (Nanoscale, 2010, 2: 429–433), salt template (Journal of Electroanalytical Chemistry, 2019, 836: 102–106), and liquid exfoliation with organic solvents (N-methyl-2-pyrrolidone, ethanol, and isopropanol) by grinding or ultrasonic treatment (Journal of Materials Chemistry A, 2017, 5(46): 24223-24231; ACS Appl Mater Interfaces, 2016, 8: 3482-3493). However, these methods involve multiple steps, generate environmentally harmful organic waste, and require high temperatures, leading to unnecessary waste. Most importantly, the resulting molybdenum oxide sheets are very large, much larger than the nanometer scale, which limits their application in lubricants and remains a challenge. The preparation of well-dispersible, nanoscale molybdenum oxide nanosheets is a current research direction. Summary of the Invention

[0003] To address the technical problem of large molybdenum oxide sheet size, this invention proposes an organic-inorganic hybrid molybdenum oxide nanosheet and its preparation method. The prepared organic-inorganic hybrid molybdenum oxide nanosheet has small size and good dispersibility.

[0004] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0005] An organic-inorganic hybrid molybdenum oxide nanosheet is prepared by the following steps: adding molybdenum oxide and an organic modifier to a mixed solvent, mixing and reacting, and removing the reaction solvent to obtain the organic-inorganic hybrid molybdenum oxide nanosheet; the mixed solvent includes water and ethanol.

[0006] The molybdenum oxide is orthorhombic molybdenum trioxide powder.

[0007] The organic modifier is one or a combination of two or more of alkylamines, polymeric amines, and alkyl diethanolamides.

[0008] The structural formula of the alkylamine is: C n H 2n+2 NH2 or C n H 2n-1 n is an integer between 3 and 18.

[0009] The polymer molecule amine structure is as follows: Its molecular weight is 1800-3500.

[0010] The alkyl diethanolamide has the following structure: Where R = C n H 2n+1 Or C n H 2n-1 n is an integer between 3 and 18.

[0011] The concentration of molybdenum oxide in the mixed solvent is 5-15 g / L, and the concentration of the organic modifier is 10-150 g / L.

[0012] The volume ratio of water to ethanol in the mixed solvent is (1-4):(1-4).

[0013] The reaction temperature is 30-100℃, and the reaction time is 1-24h.

[0014] The beneficial effects of this invention are as follows: The organic modifier in this invention interacts with the Mo-O in α-MoO3 through the interaction of the -NH in alkylamines or the -OH in alkyl diethanolamides to form organic-inorganic hybrid molybdenum oxide nanosheets. The reaction byproducts of this invention are only water and ethanol, which can be easily removed, greatly reducing the preparation cost and providing a new approach to preparing organic-inorganic hybrid molybdenum oxide nanosheets. The method of this invention features simple process and equipment, inexpensive and readily available raw materials, low cost, and high yield, making it suitable for large-scale industrial production. Attached Figure Description

[0015] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0016] Figure 1 X-ray diffraction (XRD) pattern of molybdenum oxide nanosheets prepared in Example 36;

[0017] Figure 2 Transmission electron microscopy (TEM) image of molybdenum oxide nanosheets prepared in Example 36 and corresponding elemental distribution maps of Mo and O;

[0018] Figure 3 X-ray photoelectron spectroscopy (XPS) of molybdenum oxide nanosheets prepared in Example 36;

[0019] Figure 4 : FTIR image of molybdenum oxide nanosheets prepared in Example 36;

[0020] Figure 5 Thermogravimetric analysis (TG) diagram of molybdenum oxide nanosheets prepared in Example 36. Detailed Implementation

[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] The specific structural formulas of alkylamines, polymer molecular amines, and alkyl diethanolamides in Examples 1-46 are shown in Table 1.

[0023] Table 1

[0024]

[0025] Example 1

[0026] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0027] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2 g of propylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-600 nm.

[0028] Example 2

[0029] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0030] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 0.8 g of propylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-600 nm.

[0031] Example 3

[0032] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0033] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 3.2 g of propylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-600 nm.

[0034] Example 4

[0035] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0036] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2.5 g of butylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0037] Example 5

[0038] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0039] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 1.0 g of butylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0040] Example 6

[0041] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0042] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 4 g of butylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0043] Example 7

[0044] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0045] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 4.5 g of octylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50–500 nm.

[0046] Example 8

[0047] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0048] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 1.8 g of octylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-500 nm.

[0049] Example 9

[0050] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0051] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.2 g of octylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-500 nm.

[0052] Example 10

[0053] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0054] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-400 nm.

[0055] Example 11

[0056] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0057] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2.6 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-400 nm.

[0058] Example 12

[0059] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0060] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 10.3 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-400 nm.

[0061] Example 13

[0062] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0063] Add 80 mL of distilled water, 20 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0064] Example 14

[0065] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0066] Add 60 mL of distilled water, 40 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0067] Example 15

[0068] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0069] Add 40 mL of distilled water, 60 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0070] Example 16

[0071] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0072] 20 mL of distilled water, 80 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at a constant temperature for 1 h. Then, the distilled water and ethanol were removed by vacuum distillation, and the mixture was dried under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0073] Example 17

[0074] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0075] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, 0.8 g of propylamine and 2.6 g of dodecylamine to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-300 nm.

[0076] Example 18

[0077] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0078] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, 1.0 g of butylamine and 2.6 g of dodecylamine to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-300 nm.

[0079] Example 19

[0080] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0081] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 8.4 g of hexadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0082] Example 20

[0083] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0084] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 3.4 g of hexadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0085] Example 21

[0086] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0087] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 13.4 g of hexadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0088] Example 22

[0089] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0090] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 9.4 g of octadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0091] Example 23

[0092] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0093] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 3.8 g of octadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0094] Example 24

[0095] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0096] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 15.0 g of octadecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0097] Example 25

[0098] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0099] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 9.3 g of oleylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0100] Example 26

[0101] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0102] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 3.7 g of oleylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0103] Example 27

[0104] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0105] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 14.9 g of oleylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-500 nm.

[0106] Example 28

[0107] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0108] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, 0.8 g of propylamine and 3.7 g of oleylamine to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0109] Example 29

[0110] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0111] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, 1.0 g of butylamine and 3.7 g of oleylamine to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0112] Example 30

[0113] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0114] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, 1.8 g of octylamine and 3.7 g of oleylamine to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0115] Example 31

[0116] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0117] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 9.4 g of polyethyleneimine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0118] Example 32

[0119] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0120] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2.5 g of polyethyleneimine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0121] Example 33

[0122] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0123] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 25 g of polyethyleneimine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0124] Example 34

[0125] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0126] 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (specific structure shown in Table 1) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at this temperature for 6 h. Then, the distilled water and ethanol were removed by vacuum distillation, and the mixture was dried under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions ranging from 10 to 200 nm. The X-ray diffraction pattern, transmission electron microscope image and elemental distribution map, X-ray photoelectron spectroscopy, infrared spectrum, and thermogravimetric analysis are shown below. Figure 1 , 2 As shown in Figures 3, 4, and 5.

[0127] The molybdenum oxide nanosheets obtained in Example 34 were tested using X-ray diffraction (XRD). See [link to XRD diagram]. Figure 1 The results showed that the (020) crystal plane of the molybdenum oxide nanosheets modified with oleic acid diethanolamide was significantly broadened compared with the diffraction peak of the α-MoO3 raw material, indicating that the grain size of the modified molybdenum oxide was smaller.

[0128] The molybdenum oxide nanosheets obtained in Example 34 were characterized using transmission electron microscopy. Figure 2 The results showed that the molybdenum oxide nanosheets had relatively uniform morphology and size, with lateral dimensions ranging from 10 to 200 nm. Elemental analysis revealed significant enrichment of Mo and O elements.

[0129] The molybdenum oxide nanosheets obtained in Example 34 were characterized by X-ray photoelectron spectroscopy to analyze their composition and chemical state. (See attached image.) Figure 3 The results demonstrated that the organic-inorganic hybrid molybdenum oxide nanosheets were composed of Mo, O, N, and C. The two characteristic peaks at 235.2 and 233.2 eV in the high-resolution XPS spectrum of Mo 3d represent the values ​​of Mo, O, N, and C, respectively. 6+ (3d 3 / 2 ) and Mo 6+ (3d 5 / 2 The two characteristic peaks of Mo 3d at 234.3 and 231.2 eV correspond to Mo 5+ (3d3 / 2 ) and Mo 5+ (3d 5 / 2 This result indicates that the molybdenum oxide nanosheets modified with oleic acid diethanolamide possess two valence states of molybdenum, which is attributed to the formation of oxygen vacancies during the reaction between oleic acid diethanolamide and molybdenum oxide. The characteristic peak of O 1s at 529.2 eV confirms the formation of oxygen vacancies.

[0130] Figure 4 In Figures a and b, the infrared spectra of the organic modifier oleic acid diethanolamide and the prepared oleic acid diethanolamide-modified molybdenum oxide nanosheets are respectively. Curve a shows that the wavelength is approximately 3302 cm⁻¹. -1 The broad peak at 2925 cm⁻¹ is the stretching vibration peak of -OH; the CH stretching vibration peaks in methyl and methylene groups appear at 2925 and 2855 cm⁻¹, respectively. -1 At 1620cm -1 The peak at 1564 cm⁻¹ is the stretching vibration peak of C=C; -1 The strong peak at 1070 cm⁻¹ is the stretching vibration peak of CN in the amide; -1 The peak is a characteristic absorption peak of CO when an alkyl group is linked to a hydroxyl group; long alkyl chains -(CH2) n The characteristic peak of (n≥4) appears at 722 cm⁻¹. -1 However, in curve b, at 819cm... -1 A Mo-O stretching vibration peak appeared at [location], and compared to 858 cm⁻¹ in α-MoO₃, [the peak value is missing]. -1 The shift in the Mo-O stretching vibration peak indicates an interaction between oleic acid diethanolamide and molybdenum oxide, which allows the organic modifier to be firmly modified on the surface of molybdenum oxide, thereby giving the prepared molybdenum oxide nanosheets good dispersion stability.

[0131] Figure 5 This is the thermogravimetric analysis (TGA) curve of oleic acid diethanolamide-modified molybdenum oxide nanosheets. The prepared nanosheets underwent continuous weight loss between 200-500℃, which corresponds to the thermal decomposition of the organic modifier within this temperature range. As shown in the figure, the organic modifier accounts for 79.5% of the weight.

[0132] Example 35

[0133] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0134] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2.6 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 10-200 nm.

[0135] Example 36

[0136] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0137] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 12.8 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 10-200 nm.

[0138] Example 37

[0139] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0140] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 30 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 50-600 nm.

[0141] Example 48

[0142] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0143] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 100 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 10-200 nm.

[0144] Example 39

[0145] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0146] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-400 nm.

[0147] Example 40

[0148] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0149] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 12 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 10-200 nm.

[0150] Example 41

[0151] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0152] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 24 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 10-200 nm.

[0153] Example 42

[0154] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0155] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 7.7 g of stearic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0156] Example 43

[0157] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0158] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 2.6 g of stearic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0159] Example 44

[0160] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0161] Add 50 mL of distilled water, 50 mL of ethanol, 1 g of α-MoO3, and 12.8 g of stearic acid diethanolamide (see Table 1 for specific structure) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 6 h. Then remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 20-300 nm.

[0162] Comparative Example 1

[0163] An organic-inorganic hybrid molybdenum oxide composite material, the preparation method of which includes the following steps:

[0164] 100 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structure) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at a constant temperature for 12 h. The ethanol was then removed by vacuum distillation and dried under vacuum at 60 °C to obtain a dodecylamine-modified molybdenum oxide composite material with a transverse dimension in the range of 100-5000 nm.

[0165] Comparative Example 2

[0166] An organic-inorganic hybrid molybdenum oxide composite material, the preparation method of which includes the following steps:

[0167] 100 mL of ethanol, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structure) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at a constant temperature for 12 h. Then, the ethanol was removed by vacuum distillation and the mixture was dried under vacuum at 60 °C to obtain oleic acid diethanolamide-modified molybdenum oxide composite material with a transverse dimension in the range of 500-3000 nm.

[0168] Comparative Example 3

[0169] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0170] Add 90 mL of distilled water, 10 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) to a 250 mL three-necked flask. Heat the mixture to 70 °C in an oil bath and react at a constant temperature for 1 h. Then, remove the distilled water and ethanol by vacuum distillation and dry under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 1000-10000 nm.

[0171] Comparative Example 4

[0172] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0173] 10 mL of distilled water, 90 mL of ethanol, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at a constant temperature for 1 h. Then, the distilled water and ethanol were removed by vacuum distillation, and the mixture was dried under vacuum at 60 °C to obtain molybdenum oxide nanosheets with lateral dimensions in the range of 500-3000 nm.

[0174] Comparative Example 5

[0175] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0176] 100 mL of distilled water, 1 g of α-MoO3, and 6.4 g of dodecylamine (see Table 1 for specific structures) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at this temperature for 12 h. After standing, the MoO3 settled at the bottom of the flask and hardly participated in the reaction. Therefore, nanosheets could not be prepared under pure water conditions.

[0177] Comparative Example 6

[0178] An organic-inorganic hybrid molybdenum oxide nanosheet was prepared by the following steps:

[0179] 100 mL of distilled water, 1 g of α-MoO3, and 7.7 g of oleic acid diethanolamide (see Table 1 for specific structures) were added to a 250 mL three-necked flask. The mixture was heated to 70 °C in an oil bath and reacted at this temperature for 12 h. After standing, the MoO3 settled at the bottom of the flask and hardly participated in the reaction. Therefore, nanosheets could not be prepared under pure water conditions.

[0180] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing organic-inorganic hybrid molybdenum oxide nanosheets, characterized in that, The process includes the following steps: adding molybdenum oxide and an organic modifier to a mixed solvent, mixing and reacting, and then removing the reaction solvent to obtain organic-inorganic hybrid molybdenum oxide nanosheets; the mixed solvent includes water and ethanol; The molybdenum oxide raw material is orthorhombic molybdenum trioxide powder; The organic modifier is one or a combination of two of polymer molecular amines and alkyl diethanolamides; The volume ratio of water to ethanol in the mixed solvent is (1-4):(1-4). The polymer molecule amine structure is as follows: .

2. The method for preparing organic-inorganic hybrid molybdenum oxide nanosheets according to claim 1, characterized in that, The alkyl diethanolamide has the following structure: Where R=C n H 2n+1 Or C n H 2n-1 n is an integer between 3 and 18.

3. The method for preparing organic-inorganic hybrid molybdenum oxide nanosheets according to claim 2, characterized in that, The concentration of molybdenum oxide in the mixed solvent is 5-15 g / L, and the concentration of the organic modifier is 10-150 g / L.

4. The method for preparing organic-inorganic hybrid molybdenum oxide nanosheets according to claim 3, characterized in that, The reaction temperature is 30-100 ℃, and the reaction time is 1-24 h.

5. Organic-inorganic hybrid molybdenum oxide nanosheets prepared by the method according to any one of claims 1-4.

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