Bismuth-Doped Bismuth Phosphate Photoelectrode Modified by Titanium Carbide and Preparation Method
20240158934 ยท 2024-05-16
Assignee
Inventors
Cpc classification
C25B11/091
CHEMISTRY; METALLURGY
C25B11/067
CHEMISTRY; METALLURGY
International classification
C25B11/091
CHEMISTRY; METALLURGY
C25B9/50
CHEMISTRY; METALLURGY
C25B11/052
CHEMISTRY; METALLURGY
Abstract
A bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide and a preparation method are provided. A first chitosan coating and a second chitosan coating both show electropositivity, and a two-dimensional Ti.sub.3C.sub.2 coating shows electronegativity, wherein the bismuth-doped bismuth phosphate photoelectrode modified by two-dimensional Ti.sub.3C.sub.2 is prepared by an electrostatic self-assembly method. The method is efficient, environment friendly and has simple operation steps; no precious metals are doped in reactions, and no pollutants are produced in reaction processes to meet a requirement of environmental protection; and the method has positive significance for putting the bismuth-doped bismuth phosphate photoelectrode modified by the titanium carbide into actual production. The bismuth-doped bismuth phosphate photoelectrode enhances synergistic effect of electrons and delays recombination time of photo-induced electrons and hole pairs. A photocurrent response value of the bismuth-doped bismuth phosphate photoelectrode is about 410 times a photocurrent response value of a pure bismuth-doped bismuth phosphate photoelectrode.
Claims
1. A method for a self-assembly preparation of a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide, comprising the following steps: S1: preparing bismuth-doped bismuth phosphate by a hydrothermal method; S2: putting the bismuth-doped bismuth phosphate prepared in step S1 into deionized water, and performing an ultrasonic vibration treatment for 0.5-1 hour to form a bismuth-doped bismuth phosphate suspension; S3: weighing a predetermined mass of chitosan, dissolving the chitosan in an acetic acid solution with a mass fraction of 2-3% to form a chitosan solution, wherein a mass fraction of the chitosan solution is 0.5-1%, and adjusting the chitosan solution to pH=5 with a 0.1 M sodium hydroxide solution; S4: cleaning and drying an indium tin oxide (ITO) glass, taking a first predetermined mass of the bismuth-doped bismuth phosphate suspension prepared in step S2, coating the bismuth-doped bismuth phosphate suspension on a conductive surface of the ITO glass, performing drying to form a first bismuth-doped bismuth phosphate coating, taking a second predetermined mass of the bismuth-doped bismuth phosphate suspension prepared in step S2 again, coating the bismuth-doped bismuth phosphate suspension on an outer surface of the first bismuth-doped bismuth phosphate coating of the ITO glass, performing drying to form a second bismuth-doped bismuth phosphate coating, then taking a first predetermined mass of the chitosan solution prepared in step S3, coating the chitosan solution on an outer surface of the second bismuth-doped bismuth phosphate coating of the ITO glass, and performing drying to form a first chitosan coating to obtain a bismuth-doped bismuth phosphate electrode; and S5: coating a predetermined mass of a two-dimensional Ti.sub.3C.sub.2 solution on an outer surface of the first chitosan coating of the bismuth-doped bismuth phosphate electrode prepared in step S4, performing drying to form a two-dimensional Ti.sub.3C.sub.2 coating, then taking second predetermined mass of the chitosan solution prepared in step S3, coating the chitosan solution on an outer surface of the two-dimensional Ti.sub.3C.sub.2 coating of the ITO glass, and performing drying to form a second chitosan coating to obtain the bismuth-doped bismuth phosphate photoelectrode modified by the titanium carbide, wherein in step S4, a bismuth-doped bismuth phosphate coating volume corresponding to the first bismuth-doped bismuth phosphate coating is 1-5 g/m.sup.2, a bismuth-doped bismuth phosphate coating volume corresponding to the second bismuth-doped bismuth phosphate coating is 1-5 g/m.sup.2, and a chitosan coating volume corresponding to the first chitosan coating is 1-2 g/m.sup.2; and in step S4, a two-dimensional Ti.sub.3C.sub.2 coating volume corresponding to the two-dimensional Ti.sub.3C.sub.2 coating is 0.2-1 g/m.sup.2, and a chitosan coating volume corresponding to the second chitosan coating is 1-2 g/m.sup.2.
2. The method according to claim 1, wherein step S1 comprises: respectively weighing 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose, putting the bismuth nitrate pentahydrate, the sodium dihydrogen phosphate dihydrate and the glucose in a container containing 15 mL of ethylene glycol, and performing the ultrasonic vibration treatment for 2-4 hours to form a reaction raw material suspension; transferring the reaction raw material suspension into a 20 mL Teflon-lined stainless steel autoclave, sealing the 20 mL Teflon-lined stainless steel autoclave to obtain a sealed 20 mL Teflon-lined stainless steel autoclave, and then, putting the sealed 20 mL Teflon-lined stainless steel autoclave into a muffle furnace to react for 24-120 hours at a temperature of 140-170? C.; and taking out the sealed 20 mL Teflon-lined stainless steel autoclave, cooling the sealed 20 mL Teflon-lined stainless steel autoclave to a room temperature, performing a high-speed centrifugation on a reactant mixed solution to collect samples, washing the samples with absolute ethanol and the deionized water until a solvent is removed completely, and putting cleaned solids into a drying box for drying for 3-6 hours at a temperature of 150-170? C. to obtain a bismuth-doped bismuth phosphate black powder.
3. The method according to claim 1, wherein in step S2, a mass concentration of the bismuth-doped bismuth phosphate suspension is 10 mg/mL; and in step S5, a mass concentration range of the two-dimensional Ti.sub.3C.sub.2 solution is 1-5 mg/mL.
4. A bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide, wherein the bismuth-doped bismuth phosphate photoelectrode modified by the titanium carbide is prepared by the method according to claim 1.
5. The bismuth-doped bismuth phosphate photoelectrode according to claim 4, wherein step S1 comprises: respectively weighing 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose, putting the bismuth nitrate pentahydrate, the sodium dihydrogen phosphate dihydrate and the glucose in a container containing 15 mL of ethylene glycol, and performing the ultrasonic vibration treatment for 2-4 hours to form a reaction raw material suspension; transferring the reaction raw material suspension into a 20 mL Teflon-lined stainless steel autoclave, sealing the 20 mL Teflon-lined stainless steel autoclave to obtain a sealed 20 mL Teflon-lined stainless steel autoclave, and then, putting the sealed 20 mL Teflon-lined stainless steel autoclave into a muffle furnace to react for 24-120 hours at a temperature of 140-170? C.; and taking out the sealed 20 mL Teflon-lined stainless steel autoclave, cooling the sealed 20 mL Teflon-lined stainless steel autoclave to a room temperature, performing a high-speed centrifugation on a reactant mixed solution to collect samples, washing the samples with absolute ethanol and the deionized water until a solvent is removed completely, and putting cleaned solids into a drying box for drying for 3-6 hours at a temperature of 150-170? C. to obtain a bismuth-doped bismuth phosphate black powder.
6. The bismuth-doped bismuth phosphate photoelectrode according to claim 4, wherein in step S2, a mass concentration of the bismuth-doped bismuth phosphate suspension is 10 mg/mL; and in step S5, a mass concentration range of the two-dimensional Ti.sub.3C.sub.2 solution is 1-5 mg/mL.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0021]
[0022]
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0023] The specific implementation modes of the present invention will be further described below with reference to the accompanying drawings and examples. The following examples are only used to illustrate the technical solutions of the present invention more clearly, and cannot be used to limit the protection scope of the present invention.
Example 1
[0024] A bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide is prepared by a method for self-assembly preparation of a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide in the present invention. The method includes the following steps:
[0025] 1. Preparation of Bismuth-Doped Bismuth Phosphate by Hydrothermal Method
[0026] 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose are weighed respectively and dissolved in 15 mL of ethylene glycol, and ultrasonic vibration treatment is performed by an ultrasonic cleaner for 2 h to form a reaction raw material suspension; the reaction raw material suspension is transferred into a 20 mL Teflon-lined stainless steel autoclave, the autoclave is sealed to react for 24 h at 140? C., and then, the autoclave is taken out and cooled to a room temperature; high-speed centrifugation is performed to collect solid samples, and the solid samples are washed with absolute ethanol and deionized water for 3 times until the solvent is completely cleaned; and the cleaned solid samples are dried in a drying box for 3 h at 150? C., so as to obtain bismuth-doped bismuth phosphate black powder.
[0027] 2. Preparation of Bismuth-Doped Bismuth Phosphate Electrode
[0028] 10 mg of bismuth-doped bismuth phosphate is weighed and dissolved in 1000 ?L of deionized water, and ultrasonic treatment is performed by the ultrasonic cleaner for 0.5 h to form a uniform bismuth-doped bismuth phosphate suspension with a concentration of 10 mg/mL; ITO glass is respectively added to absolute ethanol and deionized water, cleaned with the ultrasonic cleaner, and then taken out and dried; 10 ?L of the bismuth-doped bismuth phosphate suspension is weighed and coated on a conductive surface of the ITO glass, drying is performed by an infrared lamp to form a bismuth-doped bismuth phosphate first coating, 10 ?L of the bismuth-doped bismuth phosphate suspension is coated on the ITO again, and drying is performed to form a bismuth-doped bismuth phosphate second coating; and in order to enable the bismuth-doped bismuth phosphate to uniformly form a film on the ITO, chitosan (showing positive charge) is dropwise added to an outer surface of the bismuth-doped bismuth phosphate second coating twice, 10 ?L each time, and drying is performed to form a chitosan first coating, so as to obtain a bismuth-doped bismuth phosphate electrode, where the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate first coating is 1 g/m.sup.2, the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate second coating is 1 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan first coating is 1 g/m.sup.2.
[0029] The XRD data of the bismuth-doped bismuth phosphate black powder in Example 1 is consistent with the XRD spectrum of the bismuth-doped bismuth phosphate black powder in Example 2, which proves that the bismuth-doped bismuth phosphate is successfully prepared in Example 1.
[0030] 3. Preparation of Bismuth-Doped Bismuth Phosphate Photoelectrode Modified by Titanium Carbide
[0031] 100 ?L of a two-dimensional Ti.sub.3C.sub.2 stock solution with a concentration of 5 mg/mL purchased from a manufacturer is weighed and added to 100 ?L of deionized water to dilute the solution to 1 mg/mL; based on the effect of electrostatic adsorption, 20 ?L of two-dimensional Ti.sub.3C.sub.2 (showing negative charge) is weighed and uniformly coated on a bismuth-doped bismuth phosphate photoelectrode, drying is performed to form a two-dimensional Ti.sub.3C.sub.2 coating, chitosan (positive charge) is dropwise added to a surface of the two-dimensional Ti.sub.3C.sub.2 coating twice, 10 ?L each time, and drying is performed to form a chitosan second coating; and the chitosan second coating is put into a vacuum drying box for drying for 1 h at 40? C. under vacuum conditions, so as to obtain a bismuth-doped bismuth phosphate photoelectrode modified by self assembly of two-dimensional Ti.sub.3C.sub.2, namely a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide, where the two-dimensional Ti.sub.3C.sub.2 coating volume corresponding to the two-dimensional Ti.sub.3C.sub.2 coating is 0.2 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan second coating is 1 g/m.sup.2.
Example 2
[0032] A bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide is prepared by a method for self-assembly preparation of a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide in the present invention. The method includes the following steps:
[0033] 1. Preparation of Bismuth-Doped Bismuth Phosphate by Hydrothermal Method
[0034] 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose are weighed respectively and dissolved in 15 mL of ethylene glycol, and ultrasonic vibration treatment is performed by an ultrasonic cleaner for 3 h to form a reaction raw material suspension; the reaction raw material suspension is transferred into a 20 mL Teflon-lined stainless steel autoclave, the autoclave is sealed to react for 96 h at 160? C., and then, the autoclave is taken out and cooled to a room temperature; high-speed centrifugation is performed to collect solid samples, and the solid samples are washed with absolute ethanol and deionized water for 3 times until the solvent is completely cleaned; and the cleaned solid samples are dried in a drying box for 5 h at 160? C., so as to obtain bismuth-doped bismuth phosphate black powder.
[0035] The XRD spectrum of the bismuth-doped bismuth phosphate black powder in Example 2 is shown in
[0036] 2. Preparation of Bismuth-Doped Bismuth Phosphate Electrode (BiBiPO.sub.4)
[0037] 10 mg of bismuth-doped bismuth phosphate is weighed and dissolved in 1000 ?L of deionized water, and ultrasonic treatment is performed by the ultrasonic cleaner for 40 min to form a uniform bismuth-doped bismuth phosphate suspension with a concentration of 10 mg/mL; ITO glass is respectively added to absolute ethanol and deionized water, cleaned with the ultrasonic cleaner, and then taken out and dried; 10 ?L of the bismuth-doped bismuth phosphate suspension is weighed and coated on a conductive surface of the ITO glass, drying is performed by an infrared lamp to form a bismuth-doped bismuth phosphate first coating, 10 ?L of the bismuth-doped bismuth phosphate suspension is coated on the ITO again, and drying is performed to form a bismuth-doped bismuth phosphate second coating; and in order to enable the bismuth-doped bismuth phosphate to uniformly form a film on the ITO, chitosan (showing positive charge) is dropwise added to an outer surface of the bismuth-doped bismuth phosphate second coating twice, 10 ?L each time, and drying is performed to form a chitosan first coating, so as to obtain a bismuth-doped bismuth phosphate electrode (BiBiPO.sub.4), where the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate first coating is 2 g/m.sup.2, the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate second coating is 2 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan first coating is 1.5 g/m.sup.2.
[0038] 3. Preparation of Bismuth-Doped Bismuth Phosphate Photoelectrode Modified by Titanium Carbide
[0039] 100 ?L of a two-dimensional Ti.sub.3C.sub.2 stock solution with a concentration of 5 mg/mL purchased from a manufacturer is weighed and added to 100 ?L of deionized water to dilute the solution to 2.5 mg/mL; based on the effect of electrostatic adsorption, 20 ?L of two-dimensional Ti.sub.3C.sub.2 (showing negative charge) is weighed and uniformly coated on a bismuth-doped bismuth phosphate photoelectrode, drying is performed to form a two-dimensional Ti.sub.3C.sub.2 coating, chitosan (positive charge) is dropwise added to a surface of the two-dimensional Ti.sub.3C.sub.2 coating twice, 10 ?L each time, and drying is performed to form a chitosan second coating; and the chitosan second coating is put into a vacuum drying box for drying for 2 h at 50? C. under vacuum conditions, so as to obtain a bismuth-doped bismuth phosphate photoelectrode modified by self assembly of two-dimensional Ti.sub.3C.sub.2, namely a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide (abbreviated as Ti.sub.3C.sub.2BiPO.sub.4), where the two-dimensional Ti.sub.3C.sub.2 coating volume corresponding to the two-dimensional Ti.sub.3C.sub.2 coating is 0.5 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan second coating is 1.5 g/m.sup.2.
Example 3
[0040] A bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide is prepared by a method for self-assembly preparation of a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide in the present invention. The method includes the following steps:
[0041] 1. Preparation of Bismuth-Doped Bismuth Phosphate by Hydrothermal Method
[0042] 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose are weighed respectively and dissolved in 15 mL of ethylene glycol, and ultrasonic vibration treatment is performed by an ultrasonic cleaner for 4 h to form a reaction raw material suspension; the reaction raw material suspension is transferred into a 20 mL Teflon-lined stainless steel autoclave, the autoclave is sealed to react for 120 h at 170? C., and then, the autoclave is taken out and cooled to a room temperature; high-speed centrifugation is performed to collect solid samples, and the solid samples are washed with absolute ethanol and deionized water for 3 times until the solvent is completely cleaned; and the cleaned solid samples are dried in a drying box for 6 h at 170? C., so as to obtain bismuth-doped bismuth phosphate black powder.
[0043] The XRD data of the bismuth-doped bismuth phosphate black powder in Example 3 is consistent with the XRD spectrum of the bismuth-doped bismuth phosphate black powder in Example 2, which proves that the bismuth-doped bismuth phosphate is successfully prepared in Example 3.
[0044] 2. Preparation of Bismuth-Doped Bismuth Phosphate Electrode
[0045] 10 mg of bismuth-doped bismuth phosphate is weighed and dissolved in 1000 ?L of deionized water, and ultrasonic treatment is performed by the ultrasonic cleaner for 0.5 h to form a uniform bismuth-doped bismuth phosphate suspension with a concentration of 10 mg/mL; ITO glass is respectively added to absolute ethanol and deionized water, cleaned with the ultrasonic cleaner, and then taken out and dried; 10 ?L of the bismuth-doped bismuth phosphate suspension is weighed and coated on a conductive surface of the ITO glass, drying is performed by an infrared lamp to form a bismuth-doped bismuth phosphate first coating, 10 ?L of the bismuth-doped bismuth phosphate suspension is coated on the ITO again, and drying is performed to form a bismuth-doped bismuth phosphate second coating; and in order to enable the bismuth-doped bismuth phosphate to uniformly form a film on the ITO, chitosan (showing positive charge) is dropwise added to an outer surface of the bismuth-doped bismuth phosphate second coating twice, 10 ?L each time, and drying is performed to form a chitosan first coating, so as to obtain a bismuth-doped bismuth phosphate electrode, where the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate first coating is 5 g/m.sup.2, the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate second coating is 5 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan first coating is 2 g/m.sup.2.
[0046] 3. Preparation of Bismuth-Doped Bismuth Phosphate Photoelectrode Modified by Titanium Carbide (Ti.sub.3C.sub.2BiPO.sub.4)
[0047] 100 ?L of a two-dimensional Ti.sub.3C.sub.2 stock solution with a concentration of 5 mg/mL purchased from a manufacturer is weighed and added to 100 ?L of deionized water to dilute the solution to 4.5 mg/mL; based on the effect of electrostatic adsorption, 20 ?L of two-dimensional Ti.sub.3C.sub.2 (showing negative charge) is weighed and uniformly coated on a bismuth-doped bismuth phosphate photoelectrode, drying is performed to form a two-dimensional Ti.sub.3C.sub.2 coating, chitosan (positive charge) is dropwise added to a surface of the two-dimensional Ti.sub.3C.sub.2 coating twice, 10 ?L each time, and drying is performed to form a chitosan second coating; and the chitosan second coating is put into a vacuum drying box for drying for 3 h at 60? C. under vacuum conditions, so as to obtain a bismuth-doped bismuth phosphate photoelectrode modified by self assembly of two-dimensional Ti.sub.3C.sub.2, namely a bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide (Ti.sub.3C.sub.2BiPO.sub.4), where the two-dimensional Ti.sub.3C.sub.2 coating volume corresponding to the two-dimensional Ti.sub.3C.sub.2 coating is 1 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan second coating is 2 g/m.sup.2.
Comparative Example 1
[0048] A preparation method of a bismuth-doped bismuth phosphate photoelectrode includes the following steps:
[0049] 1. Preparation of Bismuth-Doped Bismuth Phosphate by Hydrothermal Method
[0050] 1 mmol of bismuth nitrate pentahydrate, 1 mmol of sodium dihydrogen phosphate dihydrate and 1 mmol of glucose are weighed respectively and dissolved in 15 mL of ethylene glycol, and ultrasonic vibration treatment is performed by an ultrasonic cleaner for 3 h to form a reaction raw material suspension; the reaction raw material suspension is transferred into a 20 mL Teflon-lined stainless steel autoclave, the autoclave is sealed to react for 96 h at 160? C., and then, the autoclave is taken out and cooled to a room temperature; high-speed centrifugation is performed to collect solid samples, and the solid samples are washed with absolute ethanol and deionized water for 3 times until the solvent is completely cleaned; and the cleaned solid samples are dried in a drying box for 5 h at 160? C., so as to obtain bismuth-doped bismuth phosphate black powder.
[0051] The XRD data of the bismuth-doped bismuth phosphate black powder in Comparative Example is consistent with the XRD spectrum of the bismuth-doped bismuth phosphate black powder in Example 2, which proves that the bismuth-doped bismuth phosphate is successfully prepared in Comparative Example.
[0052] 2. Preparation of Bismuth-Doped Bismuth Phosphate Electrode (BiBiPO.sub.4)
[0053] 10 mg of bismuth-doped bismuth phosphate is weighed and dissolved in 1000 ?L of deionized water, and ultrasonic treatment is performed by the ultrasonic cleaner for 40 min to form a uniform bismuth-doped bismuth phosphate suspension with a concentration of 10 mg/mL; ITO glass is respectively added to absolute ethanol and deionized water, cleaned with the ultrasonic cleaner, and then taken out and dried; 10 ?L of the bismuth-doped bismuth phosphate suspension is weighed and coated on a conductive surface of the ITO glass, drying is performed by an infrared lamp to form a bismuth-doped bismuth phosphate first coating, 10 ?L of the bismuth-doped bismuth phosphate suspension is coated on the ITO again, and drying is performed to form a bismuth-doped bismuth phosphate second coating; and in order to enable the bismuth-doped bismuth phosphate to uniformly form a film on the ITO, chitosan (showing positive charge) is dropwise added to an outer surface of the bismuth-doped bismuth phosphate second coating twice, 10 ?L each time, and drying is performed to form a chitosan first coating, so as to obtain a bismuth-doped bismuth phosphate electrode (BiBiPO.sub.4), where the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate first coating is 2 g/m.sup.2, the bismuth-doped bismuth phosphate coating volume corresponding to the bismuth-doped bismuth phosphate second coating is 2 g/m.sup.2, and the chitosan coating volume corresponding to the chitosan first coating is 1.5 g/m.sup.2.
[0054] In Examples 1-3 and Comparative Example 1, the coating volume of each coating is an effective coating volume corresponding to the dried coating.
[0055] The bismuth-doped bismuth phosphate photoelectrode modified by titanium carbide (Ti.sub.3C.sub.2BiPO.sub.4) prepared in Example 2 and the bismuth-doped bismuth phosphate electrode (BiBiPO.sub.4) prepared in Comparative Example 1 are respectively subjected to a photocurrent response test, and test results are shown in
[0056] The above examples are only the preferred examples of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.