Disclosure of Invention
Based on the technical scheme, the invention provides a technical scheme which can improve the conjugation degree of the carbon nitride and increase the photocatalytic performance of the carbon nitride.
The technical scheme is as follows:
the carbon nitride-based copolymer comprises (99-99.7%) carbon nitride chain segment and (0.03-0.1%) polyaromatic amine chain segment.
In one embodiment, the monomer for preparing the polyarylamine segment has a structure represented by formula (1):
wherein:
Ar1and Ar2Each independently is R1A substituted or unsubstituted aryl group having 6 to 20 ring atoms;
l is selected from the group consisting of a single bond, NR1By at least one R2Substituted or unsubstituted aryl having 6 to 20 ring atoms, or by R1A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;
each occurrence of R is independently selected from-H, alkyl groups having 1 to 10 carbon atoms;
R2selected from-H, alkyl having 1 to 10 carbon atoms, by R1A substituted or unsubstituted aryl group having 6 to 20 ring atoms;
R1is an amino group or an alkyl group having 1 to 10 carbon atoms.
In one embodiment, the Ar1And said Ar2Each independently selected from phenyl, biphenyl, naphthyl, anthryl or phenanthryl.
In one embodiment, each occurrence of R is independently selected from-H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or isobutyl.
In one embodiment, R is1Each occurrence is independently selected from-H, benzene substituted or unsubstituted with amino, naphthalene substituted or unsubstituted with amino, anthracene substituted or unsubstituted with amino.
In one embodiment, L is selected from the group consisting of:
indicates the attachment site;
m is 0, 1 or 2.
In one embodiment, the monomer for preparing the polyarylamine segment has a structure represented by any one of the following:
in one embodiment, the monomer for preparing the carbon nitride segment is melamine, urea or dicyanodiamine.
The present invention also provides a method for preparing the above-mentioned carbon nitride-based copolymer, comprising the steps of:
placing the monomer for preparing the carbon nitride chain segment in protective gas atmosphere, and reacting at 400-450 ℃ to prepare a precursor;
and mixing the precursor with a monomer for preparing the polyaromatic amine chain segment, placing the mixture in a protective gas atmosphere, and carrying out copolymerization reaction at the temperature of 500-600 ℃ to prepare the carbon nitride-based copolymer.
In one embodiment, the mass ratio of the monomer for preparing the carbon nitride chain segment to the monomer for preparing the arylamine chain segment is (120-6000): 1.
In one embodiment, in the step of preparing the precursor, the reaction time is 2-6 h; and/or
The reaction time of the copolymerization reaction is 2-8 h; and/or
In the step of preparing the precursor and the copolymer, after the reaction is finished, annealing in a natural cooling mode is adopted.
In one embodiment, after the precursor and the monomer for preparing the polyaromatic amine chain segment are mixed, the obtained mixture is mixed with an alcohol solvent, and after grinding and drying treatment, copolymerization reaction is carried out.
The invention also provides the application of the copolymer based on the carbon nitride as the catalyst for preparing the hydrogen peroxide by photocatalysis.
The invention has the following beneficial effects:
the photocatalytic activity of the carbon nitride is derived from a conjugated structure of the carbon nitride, the polyaromatic amine chain segment is introduced into the carbon nitride chain segment, so that a pi-pi conjugated system is prolonged and widened, and compared with pure carbon nitride, the copolymer disclosed by the invention has the advantages of wider light absorption range, narrower energy band structure, more excellent electronic property and higher separation efficiency of photo-generated electrons and holes, and finally the aim of improving the photocatalytic activity of the carbon nitride is fulfilled.
Compared with pure carbon nitride, the copolymer of the invention is used as a catalyst for preparing hydrogen peroxide by photocatalysis, the catalytic effect is better, and the catalytic effect can reach about 3 times of that of pure carbon nitride through tests. Meanwhile, the copolymer can be recycled after the photocatalytic reaction is finished, and can be recycled for multiple times, and after the copolymer is used for multiple times, the catalyst has higher photocatalytic activity according to the old catalyst, and is good in stability, green and environment-friendly. In addition, the preparation method of the copolymer is simple to operate, the raw materials are easy to obtain, and the preparation method is suitable for large-scale preparation.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, as another element may be added, unless an explicit limitation is used, such as "only," "consisting of … …," etc.
Unless mentioned to the contrary, terms in the singular may include the plural and are not to be construed as being one in number.
In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent. "substituted or unsubstituted" means that the defined group may or may not be substituted.
In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.
In the present invention, aryl means a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. Heteroaromatic ring systems or heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatom is preferably selected from N, O, S. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings.
Specifically, examples of aryl groups are: benzene, biphenyl, naphthalene, anthracene, phenanthrene and derivatives thereof. Examples of heteroaromatic groups are: furan, thiophene, pyrrole, pyrazole, carbazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine and derivatives thereof.
In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 10.
In the present invention, "' indicates a connection or a fusion site.
In the present invention, when the attachment site is not specified in the group, it means that an optional attachment site in the group is used as the attachment site; such as
Indicates that the substituent can be connected with any substituent position of the benzene ring.
The technical scheme of the invention is as follows:
the copolymer comprises a chain segment comprising (99-99.7%) of carbon nitride and (0.03-0.1%) of polyarylamine.
The photocatalytic activity of the carbon nitride is derived from a conjugated structure of the carbon nitride, the polyaromatic amine chain segment is introduced into the carbon nitride chain segment, so that a pi-pi conjugated system is prolonged and widened, and compared with pure carbon nitride, the copolymer disclosed by the invention has the advantages of wider light absorption range, narrower energy band structure, more excellent electronic property and higher separation efficiency of photo-generated electrons and holes, and finally the aim of improving the photocatalytic activity of the carbon nitride is fulfilled.
In one embodiment, the monomer for preparing the polyarylamine has a structure represented by formula (1):
wherein:
Ar1and Ar2Each independently is R1A substituted or unsubstituted aryl group having 6 to 20 ring atoms;
l is selected from the group consisting of a single bond, NR1By at least one R2Substituted or unsubstituted aryl having 6 to 20 ring atoms, or by R1A substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;
each occurrence of R is independently selected from-H, alkyl groups having 1 to 10 carbon atoms;
R2selected from-H, alkyl having 1 to 10 carbon atoms, by R1A substituted or unsubstituted aryl group having 6 to 20 ring atoms;
R1is an amino group or an alkyl group having 1 to 10 carbon atoms.
Preferably, Ar is1And said Ar2Each independently selected from phenyl, biphenyl, naphthyl, anthryl or phenanthryl. By adopting the structure, the pi-pi conjugated system is favorably prolonged and widened, and simultaneously, too large steric effect cannot be generated, so that the copolymerization reaction activity is too low, and the reaction speed is too slow. More preferably, Ar is1Is phenyl or biphenyl. Further, said Ar2Is phenyl or biphenyl. Particularly preferably, Ar1And Ar2Are all phenyl groups.
Preferably, each occurrence of R is independently selected from-H, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, or isobutyl. By adopting the structure, the reaction speed is favorably improved. Particularly preferably, said R is-H.
Preferably, said R is2Each occurrence is independently selected from-H, benzene substituted or unsubstituted with amino, naphthalene substituted or unsubstituted with amino, anthracene substituted or unsubstituted with amino. By adopting the structure, the number of amino groups can be increased, and the extension and the widening of a pi-pi conjugated system are facilitated.
In one more preferred embodiment, L is selected from any one of the following groups:
indicates the attachment site; m is 0, 1 or 2.
Particularly preferably, the monomer for preparing the polyarylamine has a structure shown in any one of the following:
the adoption of a symmetrical structure or para-position substitution of amino groups is beneficial to accelerating the reaction speed and improving the conjugation degree.
The monomer for preparing the carbon nitride chain segment is melamine, urea or dicyanodiamine.
The present invention also provides a method for preparing the above-mentioned carbon nitride-based copolymer, comprising the steps of:
placing the monomer for preparing the carbon nitride chain segment in protective gas atmosphere, and reacting at 400-450 ℃ to prepare a precursor;
and mixing the precursor with a monomer for preparing the polyaromatic amine chain segment, placing the mixture in a protective gas atmosphere, and carrying out copolymerization reaction at the temperature of 500-600 ℃ to prepare the carbon nitride-based copolymer.
The copolymer based on the carbon nitride is prepared by a heat treatment mode, so that the operation is simple and the production efficiency is high.
In one embodiment, the mass ratio of the monomer for preparing the carbon nitride chain segment to the monomer for preparing the arylamine chain segment is (120-6000): 1.
In one embodiment, after the precursor and the chain segment monomer for preparing the polyarylamine are mixed, the obtained mixture is mixed with an alcohol solvent, and after grinding and drying treatment, copolymerization reaction is carried out. The alcohol solvent is added for grinding, so that the precursor and the monomer for preparing the polyaromatic amine chain segment can be uniformly mixed. Preferably, the alcohol solvent is ethanol, and the drying treatment is vacuum drying at 60 ℃ for 4 to 12 hours.
In the present invention, the protective gas means argon or nitrogen. The heating rate is 2-10 deg.C/min.
In one embodiment, in the step of preparing the precursor, the reaction time (incubation time) is 2 to 6 hours. Further, in the step of preparing the precursor, after the reaction is finished, annealing is carried out in a natural cooling mode, and slow cooling is beneficial to crystal growth.
In one embodiment, the reaction time of the copolymerization reaction is 2h to 8 h. Further, in the step of preparing the copolymer, after the copolymerization reaction is finished, annealing is carried out in a natural cooling mode, and slow cooling is beneficial to crystal growth.
In addition, the invention also provides the application of the copolymer based on the carbon nitride as the catalyst for preparing the hydrogen peroxide by photocatalysis.
The technical solution of the present invention will be described in further detail with reference to specific examples.
Unless otherwise specified, all starting materials in the present invention are commercially available products.
In the examples which follow, PCN denotes polycarbon, the monomers used to prepare the polyarylamines being
(TAP) and PCN-TAPx (x is a number) represent the copolymers obtained in the examples.
Example 1
(1) Placing 5g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 420 ℃ at the heating rate of 2 ℃/min under the condition of argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain melem which is white.
(2) Putting 3g of melem and 1mgTAP into a mortar, adding 6mL of ethanol for soaking and grinding for a certain time, and then putting the mixture into a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the sample dried in the step (2) into a crucible with a cover, placing the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, reacting for 6h, and naturally cooling to room temperature to obtain the light brown PCN-TAP 1.
Example 2
(1) Placing 5g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 420 ℃ at the heating rate of 2 ℃/min under the condition of argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain melem which is white.
(2) Placing 3g of melem and 10mg of TAP into a mortar, adding 6mL of ethanol for soaking and grinding for a certain time, and then placing the mixture into a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the sample dried in the step (2) into a crucible with a cover, placing the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, reacting for 6h, and naturally cooling to room temperature to obtain the light brown PCN-TAP 2.
Example 3
(1) Placing 5g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 420 ℃ at the heating rate of 2 ℃/min under the condition of argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain melem which is white.
(2) Placing 3g of melem and 15mg of TAP into a mortar, adding 6mL of ethanol for soaking and grinding for a certain time, and then placing the mixture into a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the sample dried in the step (2) into a crucible with a cover, placing the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, reacting for 6h, and naturally cooling to room temperature to obtain brown PCN-TAP 3.
Example 4
(1) Placing 5g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 420 ℃ at the heating rate of 2 ℃/min under the condition of argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain melem which is white.
(2) Placing 3g of melem and 20mg of TAP into a mortar, adding 6mL of ethanol for soaking and grinding for a certain time, and then placing the mixture into a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the sample dried in the step (2) into a crucible with a cover, placing the crucible into a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere condition, reacting for 6h, and naturally cooling to room temperature to obtain brown PCN-TAP 4.
Example 5
(1) Placing 5g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 420 ℃ at the heating rate of 2 ℃/min under the condition of argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain melem which is white.
(2) 3g of melem and 30mg of TAP are placed in a mortar, then 6mL of ethanol is added for infiltration and grinding for a certain time, and then the mixture is placed in a vacuum drying oven at 60 ℃ for drying for 10 hours.
(3) And (3) placing the sample dried in the step (2) into a covered crucible, then placing the crucible into a muffle furnace, heating the sample to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, reacting for 6h, and naturally cooling the sample to room temperature to obtain the PCN-TAP5 with the color of dark brown, wherein the proportion of the formed polyarylamine chain segment in the copolymer is increased along with the increase of the addition amount of the TAP from PCN-TAP1, PCN-TAP2, PCN-TAP3, PCN-TAP4 to PCN-TAP5, and the color of the copolymer is brown and is sequentially deepened.
Comparative example 1
Placing 3g of melamine in a covered crucible, placing the crucible in a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min under the argon atmosphere, roasting, keeping the temperature for 4 hours, naturally cooling to room temperature to obtain a solid, and grinding the solid to obtain faint yellow PCN powder.
Test section
1. Structural analysis of PCN and PCN-TAPx:
(1)XRD:
fig. 1 shows XRD patterns of PCN and PCN-TAPx, and it can be seen from fig. 1 that two characteristic diffraction peaks can be shown at both 2 θ ° and 27.4 °, which are consistent with standard card (JCPDS-87-1526) and correspond to (100) and (002) crystal planes, respectively. In addition, as can also be seen from fig. 1, as the amount of TAP added gradually increases, the intensity of the diffraction peak at 27.4 ° is gradually weakened and then weakened to some extent and then increased compared with that of the pure PCN, which may be attributed to the fact that the degree of polymerization of the PCN itself is changed by the introduction of TAP, resulting in that the crystallinity of the catalyst becomes decreased and then increased.
(2) Infrared:
FIG. 2 is a Fourier Infrared (FTIR) spectrum of PCN and PCN-TAPx, as can be seen from FIG. 2, with PCN at 812cm-1There is an absorption peak, which is a peak of stretching vibration caused by the s-triazine structure. Comparison of the IR spectra of PCN-TAPx and PCN revealed that five of them were at 812cm-1The peak position of (a) was very high and there was no offset, indicating that copolymerization with TAP did not cause damage to the structure of carbon nitride. At the same time, 1243cm-1、1315cm-1、1400cm-1、1460cm-1、1637cm-1The infrared absorption peak appeared here is a peak of a C-N (-C) -C or C-NH-C unit. Finally, PCN and PCN-TAPx were at 3194cm-1There is a very broad peak, which is caused by the stretching vibration of N-H, indicating that there is a part of-NH or-NH in the backbone of PCN itself2Functional groups (see the random Ionotheral Copolymerization of TCNQ with PCN Semiconductor for Enhanced Photoclalyticic Full Water Splitting)。
(3) Ultraviolet:
FIG. 3 shows UV-vis-DRS spectra of PCN and PCN-TAPx, and it can be seen from FIG. 3 that PCN-TAPx has a wider light absorption range and red shift of absorption wavelength compared to PCN. Meanwhile, with the increase of the proportion of the polyaromatic amine chain segment in the copolymer, the red shift effect is more obvious, and even the copolymer has a certain absorption to light in a near infrared region.
(4) Fluorescence:
FIG. 4 is a Photoluminescence (PL) spectrum of PCN and PCN-TAP1, PCN-TAP3 and PCN-TAP5, and it can be seen from FIG. 4 that the fluorescence intensity of PCN is very high, indicating that the photogenerated electrons and holes of the linear PCN are easily recombined and the carrier separation rate is low. The fluorescence intensity of the obtained PCN-TAP1, PCN-TAP3 and PCN-TAP5 is obviously reduced after copolymerization modification, which shows that the recombination of electrons and holes of the carbon nitride is more difficult and the separation efficiency is greatly improved after TAP copolymerization is introduced.
2. Applications of
(1) Catalytic generation of hydrogen peroxide using PCN and PCN-TAPx as photocatalysts
10mg of the catalyst was placed in a custom-made 50mL quartz bottle, into which 5mL of isopropanol and 45mL of deionized water were added, respectively, and oxygen was introduced for 30 minutes. Then sealing the membrane by using a rubber plug, respectively placing the membrane in a dark place for 30 minutes by ultrasound, stirring the membrane for 30 minutes to enable oxygen to reach adsorption-desorption balance, then reacting the membrane in a multichannel, taking a sample every 30 minutes, taking about 4mL of solution out of a quartz bottle by using a syringe during sampling, and then placing a disposable filter membrane on the syringe, wherein the purpose of the filter membrane is to separate a solid catalyst from the solution so as to prevent the influence on the test effect when the iodine method is used for measuring the hydrogen peroxide. Finally, 3mL of the solution was taken by a pipette into a glass vial, and 1mL of a 0.1M potassium hydrogen phthalate solution and 0.4M potassium iodide solution were added thereto, respectively, to obtain a mixed solution. And oscillating the mixed solution for 1-2 minutes, placing the mixed solution in the dark for 1 hour, measuring the absorbance of the mixed solution at 350nm, and finally calculating the hydrogen peroxide amount of the catalyst in different time periods.
FIG. 5 shows the results of photocatalytic hydrogen peroxide production by PCN and PCN-TAPx catalysts under visible light (λ >400nm) irradiation. As can be seen from fig. 5, the photocatalytic hydrogen peroxide generation performance of PCN-TAPx is improved to different degrees relative to PCN, and as the amount of TAP added increases, the hydrogen peroxide generation capacity of the corresponding catalyst increases gradually to reach a maximum value, and then decreases. After 3 hours, about 6. mu. mol of hydrogen peroxide was catalytically produced with PCN, about 10.2. mu. mol of hydrogen peroxide was catalytically produced with PCN-TAP1, about 11.9. mu. mol of hydrogen peroxide was catalytically produced with PCN-TAP2, about 18.5. mu. mol of hydrogen peroxide was catalytically produced with PCN-TAP3, about 13.3. mu. mol of hydrogen peroxide was catalytically produced with PCN-TAP4, and about 7.2. mu. mol of hydrogen peroxide was catalytically produced with PCN-TAP5, and it was found that the catalyst No. PCN-TAP3 exhibited the most significant lifting effect, producing about 18. mu.5 mol of hydrogen peroxide, and exhibited three times as much catalytic performance as PCN.
2. Cyclic use performance of PCN-TAPx as photocatalyst for catalyzing generation of hydrogen peroxide
(1) For the first experiment: 10mg of the catalyst was placed in a custom-made 50mL quartz bottle, into which 5mL of isopropanol and 45mL of deionized water were added, respectively, and oxygen was introduced for 30 minutes. Then sealing the membrane by using a rubber plug, respectively placing the membrane in a dark place for 30 minutes by ultrasound, stirring the membrane for 30 minutes to enable oxygen to reach adsorption-desorption balance, then reacting the membrane in a multichannel, taking a sample every 30 minutes, taking about 4mL of solution out of a quartz bottle by using a syringe during sampling, and then placing a disposable filter membrane on the syringe, wherein the purpose of the filter membrane is to separate a solid catalyst from the solution so as to prevent the influence on the test effect when the iodine method is used for measuring the hydrogen peroxide. Finally, 3mL of the solution was taken by a pipette into a glass vial, and 1mL of a 0.1M potassium hydrogen phthalate solution and 0.4M potassium iodide solution were added thereto, respectively, to obtain a mixed solution. And oscillating the mixed solution for 1-2 minutes, placing the mixed solution in the dark for 1 hour, measuring the absorbance of the mixed solution at 350nm, finally calculating the hydrogen peroxide amount generated by the catalyst in different time periods, and reserving the residual solid-liquid mixture in the centrifugal tube for later use.
(2) For the second experiment: and carrying out suction filtration on the solid-liquid mixture in the quartz bottle and the solid-liquid mixture in the centrifuge tube for the first experiment to separate the solid from the liquid, drying the filter paper (the catalyst is arranged on the filter paper), repeating the first experiment on the obtained catalyst, testing the performance of producing hydrogen peroxide, and reserving the residual solid-liquid mixture in the centrifuge tube for later use.
(3) For the third experiment: and carrying out suction filtration on the solid-liquid mixture in the quartz bottle and the solid-liquid mixture in the centrifuge tube for the second experiment to separate the solid from the liquid, drying the filter paper (the catalyst is arranged on the filter paper), repeating the first experiment on the obtained catalyst, testing the performance of producing hydrogen peroxide, and reserving the residual solid-liquid mixture in the centrifuge tube for later use.
FIG. 6 shows the results of the cycle test of PCN-TAP3 catalyzed hydrogen peroxide generation, and it can be seen from FIG. 6 that the catalyst has higher photocatalytic activity and good stability of PCN-TAP3 after 3 times of use.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.