CN109897169A - A kind of triazine skeleton polymer and preparation method thereof containing alkynyl - Google Patents
A kind of triazine skeleton polymer and preparation method thereof containing alkynyl Download PDFInfo
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- CN109897169A CN109897169A CN201910212577.1A CN201910212577A CN109897169A CN 109897169 A CN109897169 A CN 109897169A CN 201910212577 A CN201910212577 A CN 201910212577A CN 109897169 A CN109897169 A CN 109897169A
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Abstract
The invention discloses a kind of triazine skeleton polymer and preparation method thereof containing alkynyl.The polymer carries out polymerization reaction by triaizine compounds and end alkynyl radical nucleopilic reagent and is made, the end alkynyl radical nucleopilic reagent refers to the aromatic structure compound for containing at least two end alkynyl radical substituent group, the end alkynyl radical substituent group is the substituent group that an alkynyl or multiple alkynyls are connected to form, and is wherein replaced with acid hydrogen by the metal with nucleophilicity on terminal acetylene.This method is using the monomer containing triazine and the reaction of the nucleopilic reagent containing Terminal Acetylenes, the triazine ring of construction feature from source.The method of the present invention preparation process is simple, and reaction temperature and reaction system are easy to accomplish when production, does not have particular/special requirement to consersion unit, has advantage in industrialization large scale preparation, more suitable for industrialized production.
Description
Technical field
The invention belongs to organic chemical synthesis technical fields, and in particular to a kind of triazine skeleton polymer containing alkynyl and its
Preparation method.
Background technique
Graphene (Graphene) is the allotrope for arranging a kind of carbon of atom with hexagonal lattice comprising single layer, it
It is the semiconductor between a kind of conduction band (Conduction Band, CB) and valence band (Valence Band, VB) with very little band gap
Material.Due to the unique structure of graphene, so that it is in electronics, optics, thermodynamics, machinery and biologically with extensive
Using and application potential.
1987, Baughman et al. theoretically predicted to contain sp2With the graphite alkene (graphynes) of sp hydridization carbon,
The structure of graphite alkene can be regarded as in graphene that partly or completely carbon-carbon single bond is replaced by triple carbon-carbon bonds, due to graphite
The reservation of aromatic rings when change, prediction graphite alkene thermodynamic stability with higher (J.Chem.Phys., 1987,87 (11),
6687-6699)。
2010, YuLiang Li et al. people using six acetylenylbenzenes be coupled method on Cu foil (pyridine, 72 hours, 60
DEG C, under nitrogen protection) synthetic graphite diine (Graphydiyne, GDY), the GDY of synthesis is with the face for being up to 3.61 square centimeters
Product, the electro-chemical test for being prepared into device show semiconductor property (Chem.Comm., 2010,46,3256-3258), from
This, about graphite diine in ion battery, the report of catalysis, Water warfare and solar battery etc. application largely occurs.
Graphite alkene/graphite the diine etc. being only made of carbon atom, since the presence of alkynyl makes the electricity of carbon atom therein
Negativity is different, is the material of non-zero band gap (nonzero band gap), calculation result table so as to cause graphite alkene/graphite diine
Bright, the material band gap of graphite alkene one kind is in 0.5eV or so.Nitrogen and carbon difference electronegativity, doping nitrogen can effectively change material
Band gap provides relevant defect (defect of offer is usually the active site being catalyzed).But in the prior art for N doping
Graphite alkene/graphite diine mostly uses the method incorporation decomposed containing nitrogen precursor, and micro-structure is not easy to control, and the graphite alkene used
Class product is excessively single.
Summary of the invention
It is an object of the present invention to provide the triazine skeleton polymers and preparation method thereof containing alkynyl, mainly solve existing skill
Such polymer architecture is single in art, it is difficult to derivatization, pore structure defect not abundant.
Used technical solution is as follows to solve above-mentioned technical problem by the present invention:
A kind of triazine skeleton polymer containing alkynyl, the polymer pass through triaizine compounds and end alkynyl radical shown in formula (I)
Nucleopilic reagent carries out polymerization reaction and is made,
Wherein, aaa, bbb, ccc are selected from halogen；
The end alkynyl radical nucleopilic reagent refers to the aromatic structure compound for containing at least two end alkynyl radical substituent group, the end
Alkynyl substituted base is the substituent group that an alkynyl or multiple alkynyls are connected to form, and wherein has acid hydrogen quilt on terminal acetylene
Metal with nucleophilicity replaces.
Preferably, the end alkynyl radical nucleopilic reagent, which is reacted by terminal alkyne compound monomer with nucleopilic reagent, is made, the Terminal Acetylenes
Compound monomer is selected from following compound 1-19,
Wherein, m, n, o, p, q, r are positive integer；Aa, bb, cc, dd, ee, ff, gg, hh, ii, jj, kk, ll are selected from hydrogen, alkane
Base, alkoxy；
Preferably, the nucleopilic reagent is selected from organolithium reagent, and organomagnesium reagent, organic zinc reagent, organic mercury reagent has
Machine copper reagent, organoaluminum reagents, Organogallium reagent, organic germanium reagent, organotin reagent, organic dithizone.
Preferably, the triaizine compounds are 2,4,6- tri- chloro-1,3,5-triazines.
The preparation method of the present invention also provides the described triazine skeleton polymer containing alkynyl, the method includes walking as follows
It is rapid:
Step 1, it prepares end alkynyl radical nucleopilic reagent: terminal alkyne compound monomer being reacted with nucleopilic reagent, end alkynyl radical nucleophilic is made
Reagent；
Step 2, polymerization reaction: triaizine compounds and the end alkynyl radical nucleopilic reagent of preparation are mixed in reaction dissolvent, nothing
Water anaerobic, the lower reaction of inert atmosphere protection, obtains reaction mixture；
Step 3, it post-processes: reaction mixture described in step 2 is added in quencher, filter residue is obtained by filtration, washes and dries
Filter residue obtains the triazine skeleton polymer containing alkynyl.
Preferably, the triaizine compounds are 2,4,6- tri- chloro-1,3,5-triazines；Polymerization reaction time is 2 hours.
Preferably, in the polymerization reaction of step 2,
When the end alkynyl radical substituent group containing there are two in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine
The molar ratio that the reaction of compound is added is 3:2；
When the end alkynyl radical substituent group containing there are three in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine
The molar ratio that the reaction of compound is added is 1:1；
When the end alkynyl radical substituent group containing there are six in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine
The molar ratio that the reaction of compound is added is 1:2.
Preferably, the reaction dissolvent of the step 2 is selected from diethylene glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, first
Benzene, glycol dimethyl ether.
Preferably, the inert atmosphere of the step 2 is selected from argon gas, helium, nitrogen.
Preferably, the quencher of the step 3 is selected from water, saturated aqueous ammonium chloride, saturated sodium-chloride water solution or alcohol.
Preferably, the solvent in the step 3 for cleaning is selected from diethylene glycol dimethyl ether, water, Isosorbide-5-Nitrae-dioxane, second
Acetoacetic ester, methanol, ethyl alcohol.
Preferably, drying temperature is 120 DEG C in the step 3, and drying time is 6 hours.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention is using the monomer containing triazine and the reaction of the nucleopilic reagent containing Terminal Acetylenes, the three of construction feature from source
Piperazine ring.Related graphite diine is first synthesized in compared with the existing technology, then mixes nitrogen with the method containing nitrogen precursor is decomposed, and this method obtains
The product structure arrived is clear, and micro-structure is controllable.
(2) the method for the present invention preparation process is simple, and reaction temperature and reaction system are easy to accomplish when production, to consersion unit
There is no particular/special requirement, there is advantage in industrialization large scale preparation, more suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 2 is the Fourier transform infrared spectroscopy figure of triazine skeleton polymer and raw material of the embodiment of the present invention 1 containing alkynyl；
Wherein label 1 indicates: the infrared spectrogram of the chloro- 1,3,5- triazine of 2,4,6- tri-；2 indicate: the Fourier of 1,4- diacetylenic benzene
Transform infrared spectroscopy figure；3 indicate: the Fourier transform infrared spectroscopy of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl
Figure；
Fig. 3 is the x-ray photoelectron spectroscopy figure of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 4 is the scanning electron microscope diagram of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 5 is the transmission electron microscope figure of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 6 is the solid 13C nuclear magnetic spectrogram of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 7 is the thermogravimetric analysis figure of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 8 is the x-ray diffractogram of powder of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Fig. 9 is the isothermal nitrogen adsorption desorption curve of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Figure 10 is the UV-vis DRS absorption spectra of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Figure 11 is the photocatalysis methyl orange discomposing effect figure of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl；
Figure 12 is the structural schematic diagram of triazine skeleton polymer of the embodiment of the present invention 2 containing alkynyl；
Figure 13 is the Fourier transform infrared spectroscopy of triazine skeleton polymer and raw material of the embodiment of the present invention 2 containing alkynyl
Figure；Wherein, label 1 indicates: the infrared spectrogram of 2,4,6- tri- chloro-1,3,5-triazines；4 indicate: 4,4 '-diacetylene biphenyl
Fourier transform infrared spectroscopy figure；5 indicate: the Fourier transformation of triazine skeleton polymer of the embodiment of the present invention 2 containing alkynyl is red
External spectrum figure；
Figure 14 is the structural schematic diagram of triazine skeleton polymer of the embodiment of the present invention 3 containing alkynyl；
Figure 15 is the Fourier transform infrared spectroscopy of triazine skeleton polymer and raw material of the embodiment of the present invention 3 containing alkynyl
Figure；Wherein, label 1 indicates: the infrared spectrogram of 2,4,6- tri- chloro-1,3,5-triazines；6 indicate: 5,5 '-diacetylenes -2,2 ' -
The Fourier transform infrared spectroscopy figure of bipyridyl；7 indicate: in Fu of triazine skeleton polymer of the embodiment of the present invention 3 containing alkynyl
Leaf transformation infrared spectrogram；
Figure 16 is the structural schematic diagram of triazine skeleton polymer of the embodiment of the present invention 4 containing alkynyl；
Figure 17 is the Fourier transform infrared spectroscopy of triazine skeleton polymer and raw material of the embodiment of the present invention 4 containing alkynyl
Figure；Wherein, label 1 indicates: the infrared spectrogram of 2,4,6- tri- chloro-1,3,5-triazines；8 indicate: tri- acetylenylbenzene of 1,3,5-
Fourier transform infrared spectroscopy figure；9 indicate: the Fourier transformation of triazine skeleton polymer of the embodiment of the present invention 4 containing alkynyl is red
External spectrum figure；
Figure 18 is the electrochemical oxygen reduction activity of triazine skeleton polymer of the embodiment of the present invention 1 containing alkynyl.
Specific embodiment
Technical solution of the present invention is described in detail below with reference to embodiment.
Embodiment 1
Using there-necked flask as reaction vessel, precise Isosorbide-5-Nitrae-diacetylenic benzene 1009mg (8mmol) is dissolved in 50mL
In super dry diethylene glycol dimethyl ether, 7mL n-BuLi/hexane solution (n-BuLi is added in nitrogen displaced air at room temperature
Concentration is 2.5mol/L, and n-BuLi mole is 17.5mmol), solution is muddy in yellow, stirs 20min, is added dropwise to and is dissolved in
The 2 of 15ml diethylene glycol dimethyl ether, 4,6- tri- chloro-1,3,5-triazines 941mg (5mmol), are warming up to 140 DEG C, are stirred to react 2h,
20mL water is added, diethylene glycol dimethyl ether, water, Isosorbide-5-Nitrae-dioxane, ethyl acetate, methanol, water cleaning filter are successively used in filtering
Slag, 110 DEG C, 6h drying obtains inclined black solid 1050mg, yield 74%.
Obtained product is tested into its Fourier transform infrared spectroscopy using the method for pressing potassium bromide troche, Fig. 1 is this implementation
Triazine skeleton polymer structural schematic diagram of the example containing alkynyl, Fig. 2 are the infrared spectrogram of polymer and raw material, wherein 1 table of label
Show: the infrared spectrogram of the chloro- 1,3,5- triazine of 2,4,6- tri-；2 indicate: the Fourier transform infrared spectroscopy of 1,4- diacetylenic benzene
Figure；3 indicate: the Fourier transform infrared spectroscopy figure of the triazine skeleton polymer containing alkynyl made from the embodiment of the present invention 1.From figure
2 it can be seen that polymeric infrared light spectrum in 850cm-1(C-Cl comes from 2,4,6- tri- chloro-1,3,5-triazines) characteristic peak disappears, with
And 835cm-1(triple carbon-carbon bonds) characteristic peak retains, meanwhile, it is located at 1360cm-1And 1497cm-1Triazine Correlative characteristic peaks occur,
Show that the triazine skeleton polymer containing alkynyl successfully synthesizes.Fig. 3 is the XPS spectrum figure of this implementation triazine product, does not find chlorine
Relevant peaks may indicate that reaction carries out complete.The morphology characterization of Fig. 4 and Fig. 5 shows that the present embodiment product has two-dimensional slice
Assembling structure.Fig. 6 is the solid core magnetic spectrum of the present embodiment, and chemical shift is that 170ppm nearby belongs to carbon in triazine, 120-
Carbon on the peak ownership phenyl ring of 140ppm, 80ppm belong to the carbon on alkynyl.Fig. 7 is the thermogravimetric analysis figure of the present embodiment, shows this
The thermal stability that embodiment polymer has had.Fig. 8 shows that the present embodiment polymer is unformed shape, can obtain it by Fig. 9 and compare table
Area is 300m2/ g or so.The present embodiment product has good optical absorption as shown in Figure 10, is used for dyestuff (methyl
Orange) in degradation experiment, 6 hours or so, Figure 11 showed that dyestuff degradation rate reaches 80%.
The electro-chemical test of 1 product of embodiment, such as Figure 18 pass it through simple heat treatment, the product after ammonia etching
With the preferable catalyst as electrocatalytic oxidation reduction, initial reduction current potential (onset potential) is 0.99V
Vs.RHE (reversible hydrogen electrode) (current density 0.1mA/cm2), half wave potential are 0.877V vs.RHE.
Embodiment 2
Using there-necked flask as reaction vessel, precise 4,4- diacetylene biphenyl 647mg (3.2mmol) is dissolved in
The super dry diethylene glycol dimethyl ether of 80mL, solution are in yellow, nitrogen displaced air, be added at room temperature 2.8mL n-BuLi/just oneself
Alkane solution (n-BuLi concentration is 2.5mol/L, and n-BuLi mole is 7mmol), there is yellow-white muddiness in solution, is added
The dilution of 20mL diethylene glycol dimethyl ether.Then, it is added dropwise to and is dissolved in 2,4,6- tri- chloro- 1, the 3,5- tri- of 15ml diethylene glycol dimethyl ether
Piperazine 376mg (2mmol), is heated to 140 DEG C, 2h.Then, be added 20mL water, filtering, successively use diethylene glycol dimethyl ether, water, 1,
4- dioxane, ethyl acetate, methanol, water clean filter residue, and 120 DEG C, 6h drying obtains inclined black solid 495mg, yield
65%.Figure 12 is the structural schematic diagram of the present embodiment product.
Figure 13 is the Fourier transform infrared spectroscopy figure of the present embodiment product, wherein polymer is infrared in 850cm-1(C-
Cl, come from 2,4,6- tri- chloro-1,3,5-triazines) characteristic peak disappearance and 825cm-1The reservation of (triple carbon-carbon bonds) characteristic peak, together
When, it is located at 1360cm-1And 1497cm-1The appearance of triazine relevant peaks shows the successful conjunction of the triazine skeleton polymer containing alkynyl
At.
Embodiment 3
Using there-necked flask as reaction vessel, 5,5 '-diacetylene -2 of precise, 2 '-bipyridyl 653mg
(3.2mmol) is dissolved in the super dry diethylene glycol dimethyl ether of 80mL, and solution is in kermesinus, and nitrogen displaced air is added at room temperature
2.8mL n-BuLi/hexane solution (n-BuLi concentration is 2.5mol/L, and n-BuLi mole is 7mmol), solution becomes
It is black, the dilution of 20mL diethylene glycol dimethyl ether is added.Then, it is added dropwise to and is dissolved in the 2,4,6- tri- chloro- of 15ml diethylene glycol dimethyl ether
1,3,5-triazines 376mg (2mmol), is heated to 140 DEG C, 2h.Then, 20mL water is added, diethylene glycol diformazan is successively used in filtering
Ether, water, Isosorbide-5-Nitrae-dioxane, ethyl acetate, methanol, water clean filter residue, and 120 DEG C, 6h drying obtains inclined black solid 488mg,
Yield 64%.Figure 14 is the present embodiment polymer architecture schematic diagram.Figure 15 is the Fourier transform infrared light of the present embodiment product
Spectrogram, wherein polymer is infrared in 850cm-1The disappearance of (C-Cl comes from 2,4,6- tri- chloro-1,3,5-triazines) characteristic peak, and
839cm-1The reservation of (triple carbon-carbon bonds) characteristic peak, meanwhile, it is located at 1360cm-1And 1497cm-1The appearance of triazine relevant peaks, equal table
The successful synthesis of the bright triazine skeleton polymer containing alkynyl.
Embodiment 4
Using there-necked flask as reaction vessel, precise 1,3, tri- acetylenylbenzene 330mg (2.2mmol) of 5- is dissolved in
The super dry diethylene glycol dimethyl ether of 80mL, solution are in yellow, nitrogen displaced air, be added at room temperature 2.8mL n-BuLi/just oneself
Alkane solution (n-BuLi concentration is 2.5mol/L, and n-BuLi mole is 7mmol), solution becomes milky.Then, it is added dropwise
Enter to be dissolved in the 2 of 20ml diethylene glycol dimethyl ether, 4,6- tri- chloro-1,3,5-triazines 376mg (2mmol) are heated to 140 DEG C, 2h.With
Afterwards, 20mL water is added, diethylene glycol dimethyl ether, water, Isosorbide-5-Nitrae-dioxane, ethyl acetate, methanol, water cleaning are successively used in filtering
Filter residue, 120 DEG C, 6h drying obtains inclined black solid.Figure 16 is the present embodiment polymer architecture schematic diagram.Figure 17 is this implementation
The Fourier transform infrared spectroscopy figure of example product, wherein polymer is infrared in 850cm-1(C-Cl comes from 2,4,6- tri- chloro- 1,3,
5- triazine) characteristic peak disappearance and 884cm-1The reservation of (triple carbon-carbon bonds) characteristic peak, meanwhile, it is located at 1360cm-1With
1497cm-1The appearance of triazine relevant peaks shows the successful synthesis of the triazine skeleton polymer containing alkynyl.
It above are only part preferred embodiment of the invention, the present invention is not limited in the content of embodiment.For ability
For technical staff in domain, can there are various change and change in the conception range of technical solution of the present invention, made
What changes and change, within that scope of the present invention.
Claims (10)
1. a kind of triazine skeleton polymer containing alkynyl, which passes through triaizine compounds shown in formula (I) and end alkynyl radical parent
Core reagent carries out polymerization reaction and is made,
Wherein, aaa, bbb, ccc are selected from halogen；
The end alkynyl radical nucleopilic reagent refers to the aromatic structure compound for containing at least two end alkynyl radical substituent group, the end alkynyl radical
Substituent group is the substituent group that an alkynyl or multiple alkynyls are connected to form, and wherein on terminal acetylene there is acid hydrogen to be had
The metal of nucleophilicity replaces.
2. the triazine skeleton polymer containing alkynyl as described in claim 1, it is characterised in that: the end alkynyl radical nucleopilic reagent by
Terminal alkyne compound monomer is reacted with nucleopilic reagent to be made, and the terminal alkyne compound monomer is selected from following compound 1-19,
Wherein, m, n, o, p, q, r are positive integer；Aa, bb, cc, dd, ee, ff, gg, hh, ii, jj, kk, ll be selected from hydrogen, alkyl,
Alkoxy.
3. the triazine skeleton polymer containing alkynyl as claimed in claim 2, it is characterised in that: the nucleopilic reagent is selected from organic
Lithium reagent, organomagnesium reagent, organic zinc reagent, organic mercury reagent, organic copper reagent, organoaluminum reagents, Organogallium reagent are organic
Germanium reagent, organotin reagent, organic dithizone.
4. the triazine skeleton polymer containing alkynyl as described in claim 1, it is characterised in that: the triaizine compounds are 2,4,
The chloro- 1,3,5- triazine of 6- tri-.
5. the preparation method of the described in any item triazine skeleton polymers containing alkynyl of claim 1-4, which is characterized in that described
Method includes the following steps:
Step 1, it prepares end alkynyl radical nucleopilic reagent: terminal alkyne compound monomer being reacted with nucleopilic reagent, the examination of end alkynyl radical nucleophilic is made
Agent；
Step 2, polymerization reaction: triaizine compounds and the end alkynyl radical nucleopilic reagent of preparation are mixed in reaction dissolvent, anhydrous nothing
Oxygen, the lower reaction of inert atmosphere protection, obtains reaction mixture；
Step 3, it post-processes: reaction mixture described in step 2 is added in quencher, filter residue is obtained by filtration, washes and dries filter residue,
Obtain the triazine skeleton polymer containing alkynyl.
6. the preparation method of the triazine skeleton polymer containing alkynyl as claimed in claim 5, it is characterised in that: in step 2
In polymerization reaction,
When the end alkynyl radical substituent group containing there are two in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine chemical combination
The molar ratio that the reaction of object is added is 3:2；
When the end alkynyl radical substituent group containing there are three in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine chemical combination
The molar ratio that the reaction of object is added is 1:1；
When the end alkynyl radical substituent group containing there are six in end alkynyl radical nucleopilic reagent, the end alkynyl radical nucleopilic reagent and the triazine chemical combination
The molar ratio that the reaction of object is added is 1:2.
7. the preparation method of the triazine skeleton polymer containing alkynyl as claimed in claim 5, it is characterised in that: the step 2
Reaction dissolvent be selected from diethylene glycol dimethyl ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, toluene, glycol dimethyl ether.
8. the preparation method of the triazine skeleton polymer containing alkynyl as claimed in claim 5, it is characterised in that: the step 2
Inert atmosphere be selected from argon gas, helium, nitrogen.
9. the preparation method of the triazine skeleton polymer containing alkynyl as claimed in claim 5, it is characterised in that: the step 3
Quencher be selected from water, saturated aqueous ammonium chloride, saturated sodium-chloride water solution or alcohol.
10. the preparation method of the triazine skeleton polymer containing alkynyl as claimed in claim 5, it is characterised in that: the step 3
In for cleaning solvent be selected from diethylene glycol dimethyl ether, water, Isosorbide-5-Nitrae-dioxane, ethyl acetate, methanol, ethyl alcohol.
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| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114588942A (en) * | 2022-02-25 | 2022-06-07 | 呼和浩特市联合鼎盛固体废物处理有限公司 | Solar hydrogen production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113578362A (en) * | 2021-07-23 | 2021-11-02 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN113578362B (en) * | 2021-07-23 | 2023-09-08 | 上海工程技术大学 | Preparation method and application of alkynyl-modified semiconductor material |
| CN114588942A (en) * | 2022-02-25 | 2022-06-07 | 呼和浩特市联合鼎盛固体废物处理有限公司 | Solar hydrogen production method |
| CN114588942B (en) * | 2022-02-25 | 2023-10-13 | 呼和浩特市联合鼎盛固体废物处理有限公司 | Method for producing hydrogen by solar energy |
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