CN103240119A - Chirality graphite phase carbon nitride polymer semiconductor photocatalyst - Google Patents
Chirality graphite phase carbon nitride polymer semiconductor photocatalyst Download PDFInfo
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Abstract
The invention discloses a chirality graphite phase carbon nitride polymer semiconductor photocatalyst as well as a preparation method and applications thereof, and belongs to the technical field of material preparation and photocatalysis. Chirality graphite phase carbon nitride is synthesized by taking cyanamide as a precursor and chirality mesoporous silica as a hard template, and removing the template through heat polymerization. The chirality graphite phase carbon nitride prepared by the invention has a chirality spiral-bar-shaped morphology and a micro-nano structure, shows particular circular dichroism and optical activity by when being compared with traditional body phase carbon nitride, has a great specific surface area and a high optical absorption performance, and shows a favorable optical catalysis hydrogen generating performance under visible light. According to the invention, the chirality graphite phase carbon nitride polymer semiconductor photocatalyst is synthesized; a preparation technology is improved; and the chirality graphite phase carbon nitride polymer semiconductor photocatalyst as well as the preparation method and applications thereof have an important application prospect.
Description
Technical field
The invention belongs to material preparation and photocatalysis technology field, be specifically related to a kind of chirality graphite phase carbon nitride polymer semiconductor photochemical catalyst and its preparation method and application.
Background technology
If a kind of material does not overlap with its mirror image, we just claim it to have chirality, and this material is called chiral material.Chiral material extensively is present in nature and the artificial synthetic material and medicine.Because it has important function at aspects such as material, catalysis, sensing, molecular recognition, artificial synthesis of chiral material has great importance.At present, people have prepared silica, metal oxide, gold atom bunch, molecular sieve, metal-organic framework material, organic matter, polymer of chirality etc.Wherein more typical example is chirality mesoporous earth silicon material.Recently, people such as Che Shunai successfully synthesize Metaporous silicon dioxide material (Nature, 2004,429,281 with chiral helical structure; Adv. Mater. 2006,18, and 593; Chem. Eur. J. 2008,14, and 6413).Because chirality silica has the duct of exquisite pattern, rule, big specific area and good physical and chemical stability, it can be used as a kind of hard template and transmits chirality and synthetic new chiral material.
In recent years, graphite phase carbon nitride semi-conducting polymer material receives scientist and researchers' concern (Nat. Mater. 2009,8,76) as a kind of metal-free visible-light photocatalyst.But because it is body phase material, defective is many, and specific area is little, and active sites is few, has influenced its quantum efficiency and photocatalytic activity.So people wish to improve its photocatalytic activity by structure and the pattern of control carbonitride.A large amount of work has been done in structure and the pattern regulation and control of carbonitride by our seminar, as (Adv. Funct. Mater. 2013, doi:10.1002/adfm.201203287 such as the synthetic order mesoporous carbonitride of SBA-15 type, spherical carbonitrides; Nature Communications 2012,3,1139).But the research work of the micro-nano structure of chirality and spiral being introduced carbonitride does not appear in the newspapers as yet.Carbonitride is carried out the chirality regulation and control, is a kind of brand-new modifying and decorating means, is expected to change its structural parameters and optics, electricity, photocatalysis performance.Chiral helical graphite phase carbon nitride polymeric material will have wide practical use in fields such as chirality photoswitch, molecular recognition, selective absorption separation, sensor and catalysis.In addition, chirality is delivered to the polymer carbonitride from inorganic material silica, has realized the chirality reproduction process on the materialogy, have important directive function for the synthesis of chiral material.
Summary of the invention
The object of the present invention is to provide a kind of chirality graphite phase carbon nitride polymer semiconductor photochemical catalyst and its preparation method and application.The chirality graphite phase carbon nitride of the present invention's preparation has the bar-shaped pattern of chiral helical and micro-nano structure, compare with traditional body phase carbon nitride, show special circular dichroism and optical activity, have bigger specific area and stronger absorbing properties, under visible light, show good photocatalysis and produce the hydrogen performance.
For achieving the above object, the present invention adopts following technical scheme:
A kind of chirality graphite phase carbon nitride polymer semiconductor photochemical catalyst is the semi-conducting polymer with the bar-shaped pattern of chiral helical and micro-nano structure, and chemical formula is C
3N
4, and be class graphite phase, specific area is 50-100 m
2/ g absorbs visible light, and the light absorption band edge is at 450-600 nm, and has the performance that photochemical catalyzing is produced hydrogen, can be used as a kind of photochemical catalyst, has special circular dichroism and optical activity simultaneously.
The method for preparing aforesaid chirality graphite phase carbon nitride polymer semiconductor photochemical catalyst is to be that predecessor and chirality mesoporous silica are hard template with the cyanamide, carries out thermal polymerization, removes template, obtains chirality graphite phase carbon nitride polymer.May further comprise the steps:
(1) (Adv. Mater. 2006,18,593 for the synthesis of chiral mesoporous silicon oxide; Chem. Eur. J. 2008,14, and 6413).L-alanine (or D-alanine), sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1 ~ pH5, stir, washing, oven dry obtains C
14-L-AlaA (or C
14-D-AlaA).Get 0.3g ~ 1g C
14-L-AlaA (or C
14-D-AlaA) add 1g ~ 15g water and 1g ~ 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 1g ~ 10gHCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g ~ 5.46g 3-aminopropyl triethoxysilane and 1.46g ~ 6.23g ethyl orthosilicate, stir 0.5h, left standstill 1 ~ 3 day, centrifugal, washing, oven dry.
(2) with chirality mesoporous silica in 450 ℃ ~ 600 ℃ roasting 1 ~ 10h, grind, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.
(3) in round-bottomed flask, adding mass ratio is the cyanamide of 8:1 ~ 6:1 and the chirality mesoporous silica of step (2), vacuumizes, heating and ultrasonic 60 ℃ ~ 90 ℃ stirrings; Precipitation is got in washing, and oven dry is ground; With pressed powder in N
2450 ℃ ~ 600 ℃ roasting 1h ~ 10h in the atmosphere; Add 4 mol/L ammonium hydrogen fluoride solutions in the solid after the roasting, washing, oven dry namely gets chirality graphite phase carbon nitride polymer.
Described chirality graphite phase carbon nitride polymer applications photochemical catalyzing under visible light is produced hydrogen, and hydrogen-producing speed is 7 times of body phase graphite phase carbon nitride.
Remarkable advantage of the present invention is:
(1) the present invention has synthesized the graphite phase carbon nitride polymer with chirality pattern and nanostructured first, and shows special circular dichroism and the optical activity that is different from traditional carbon nitride material.
(2) the chirality graphite phase carbon nitride polymer that synthesizes of the present invention containing metal not has advantages such as cheapness, environmental protection, stable, light weight.
(3) preparation method of the present invention can be effectively copies to the chirality of silica in the carbonitride, and is applicable to the carbonitride of synthetic other patterns and micro-nano structure, has good Modulatory character and broad spectrum activity.
(4) the present invention is applied to photocatalysis with the chiral helical polymeric material first and produces hydrogen, find that the chirality regulation and control are conducive to improve the photocatalysis product hydrogen performance of carbonitride, and the chirality carbonitride has good activity stability.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.
Fig. 2 is the solid of the chirality graphite phase carbon nitride of embodiment 1 gained
13The C nuclear magnetic resonance (
13C NMR) figure.
Fig. 3 is ESEM (SEM) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.
Fig. 4 is transmission electron microscope (TEM) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.
Fig. 5 is solid diffuse reflection circular dichroism (DRCD) and the ultraviolet-visible absorption spectroscopy figure of the chirality graphite phase carbon nitride of embodiment 1 gained, and compares with traditional body phase carbon nitride.
Fig. 6 is that the chirality graphite phase carbon nitride of embodiment 1 gained and traditional body phase carbon nitride carry out the performance comparison diagram that photochemical catalyzing is produced hydrogen.
In above-mentioned figure, a represents prepared chirality graphite phase carbon nitride; B represents traditional body phase carbon nitride.
The specific embodiment
Below be several embodiments of the present invention, further specify the present invention, but the present invention is not limited only to this.
Embodiment 1
L-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-L-AlaA.Get 0.3g C
14-L-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 6:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
Embodiment 2
L-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-L-AlaA.Get 0.3g C
14-L-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 7:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
Embodiment 3
L-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-L-AlaA.Get 0.3g C
14-L-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 8:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
D-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-D-AlaA.Get 0.3g C
14-D-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 6:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
Embodiment 5
D-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-D-AlaA.Get 0.3g C
14-D-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 7:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
Embodiment 6
D-alanine, sodium hydroxide solution, 30% acetone soln are mixed, under 0 ℃, drip myristyl acyl chlorides and NaOH solution respectively, keep pH 12, after reaction finishes, add HCl solution and regulate pH 1, stir, washing, oven dry obtains C
14-D-AlaA.Get 0.3g C
14-D-AlaA adds 10g water and 10g NaOH (0.1mol/L) solution, the stirring at room dissolving, add 10g HCl (0.01mol/L) solution again, 22 ℃ are stirred 1h down, add the mixture of 0.23g 3-aminopropyl triethoxysilane and 1.46g ethyl orthosilicate, stir 0.5h, left standstill 1 day, centrifugal, washing, oven dry.Chirality mesoporous silica in 550 ℃ of roasting 6h, is ground, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground.In round-bottomed flask, the chirality mesoporous silica (mass ratio is 8:1) that adds cyanamide and handled vacuumizes, heating and ultrasonic, 60 ℃ of stirrings.Precipitation is got in washing, and oven dry is ground.With pressed powder in N
2550 ℃ of roasting 4h in the atmosphere.Solid after the roasting adds 4 mol/L ammonium hydrogen fluoride solutions, washing, and the chirality carbonitride has just been synthesized in oven dry.
Performance test
Fig. 1 is X-ray powder diffraction (XRD) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.Can find that from figure the chirality carbonitride is 13.1
oWith 27.6
oTwo XRD diffraction maximums that significantly belong to graphite phase carbon nitride (100) and (002) crystal face appear in the place, confirm that the product of preparation is the graphite phase carbon nitride.
Fig. 2 is the solid of the chirality graphite phase carbon nitride of embodiment 1 gained
13The C nuclear magnetic resonance (
13C NMR) figure.Can find that from figure the chirality carbonitride two tangible nuclear magnetic resonance peaks occur at 155.6 ppm and 164.3 ppm, belong to C (i) in the graphite phase carbon nitride seven piperazine ring structure unit and the chemical shift of C (e) respectively, confirm that the product of preparation is the graphite phase carbon nitride.
Fig. 3 is ESEM (SEM) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.Can find that from figure chirality graphite phase carbon nitride has the bar-shaped pattern of uniform chiral helical, about 100 ~ 200 nm of diameter of rod, length is at 0.5 ~ 2 μ m, and has left-handed simultaneously and rod dextrorotation.
Fig. 4 is transmission electron microscope (TEM) figure of the chirality graphite phase carbon nitride of embodiment 1 gained.Can find that from figure chirality graphite phase carbon nitride has the bar-shaped pattern of uniform chiral helical.
Fig. 5 is solid diffuse reflection circular dichroism (DRCD) and the ultraviolet-visible absorption spectroscopy figure of the chirality graphite phase carbon nitride of embodiment 1 gained.Can find that from figure the light abstraction width of chirality graphite phase carbon nitride at 200-450 nm, compares with the body phase carbon nitride, absorbing band edge generation red shift and optical absorption intensity increases.Chirality graphite phase carbon nitride has positive Cotton effect at the 420nm place, shows circular dichroism, has further proved optical activity and chirality that it is special.And the body phase carbon nitride does not almost have signal in circular dichroism.
Fig. 6 is the chirality graphite phase carbon nitride of embodiment 1 gained and the performance comparison diagram that body phase carbon nitride photochemical catalyzing is produced hydrogen.Can find that from figure the hydrogen-producing speed of chirality graphite phase carbon nitride under visible light (λ〉420 nm) reaches 74 μ mol h
-1, with body phase carbon nitride (10 μ mol h
-1) compare and improved 7 times.Chirality graphite phase carbon nitride has kept higher activity stability simultaneously, does not see obvious inactivation in the reaction that reaches 16 h.
The above only is preferred embodiment of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. chirality graphite phase carbon nitride polymer semiconductor photochemical catalyst, it is characterized in that: described chirality graphite phase carbon nitride polymer has the bar-shaped pattern of chiral helical and micro-nano structure, and has circular dichroism and optical activity.
2. chirality graphite phase carbon nitride according to claim 1 polymer semiconductor photochemical catalyst, it is characterized in that: the chemical formula of carbonitride polymer is C
3N
4, and be class graphite phase, be a kind of polymer semiconductor.
3. chirality graphite phase carbon nitride according to claim 1 polymer semiconductor photochemical catalyst, it is characterized in that: the specific area of chirality graphite phase carbon nitride polymer is 50-100 m
2/ g absorbs visible light, and the light absorption band edge is at 450-600 nm.
4. method for preparing chirality graphite phase carbon nitride as claimed in claim 1 polymer semiconductor photochemical catalyst, it is characterized in that: be that predecessor and chirality mesoporous silica are hard template with the cyanamide, carry out thermal polymerization, remove template, obtain chirality graphite phase carbon nitride polymer.
5. the preparation method of chirality graphite phase carbon nitride according to claim 4 polymer semiconductor photochemical catalyst is characterized in that: may further comprise the steps:
(1) synthesis of chiral mesoporous silicon oxide;
(2) with chirality mesoporous silica in 550 ℃ of roasting 6h, grind, add 1 mol/L HCl, 80 ℃ of stirrings, centrifugal, oven dry is ground;
(3) in round-bottomed flask, adding mass ratio is the cyanamide of 8:1 ~ 6:1 and the chirality mesoporous silica of step (2), vacuumizes, heating and ultrasonic 60 ℃ ~ 90 ℃ stirrings; Precipitation is got in washing, and oven dry is ground; With pressed powder in N
2450 ℃ ~ 600 ℃ roasting 1h ~ 10h in the atmosphere; Add 4 mol/L ammonium hydrogen fluoride solutions in the solid after the roasting, washing, oven dry namely gets chirality graphite phase carbon nitride polymer.
6. the application of a chirality graphite phase carbon nitride as claimed in claim 1 polymer semiconductor photochemical catalyst, it is characterized in that: described chirality graphite phase carbon nitride polymer applications photochemical catalyzing under visible light is produced hydrogen, and hydrogen-producing speed is 7 times of body phase graphite phase carbon nitride.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623856A (en) * | 2013-12-10 | 2014-03-12 | 福州大学 | Spherical mesoporous carbon nitride photocatalyst with multistage nano structure |
| CN103638960A (en) * | 2013-12-19 | 2014-03-19 | 福州大学 | Polymer photocatalyst as well as preparation method and application thereof |
| CN103721745A (en) * | 2014-01-07 | 2014-04-16 | 福州大学 | Copolymerization modified ordered mesoporous carbon nitride photocatalyst |
| CN103861630A (en) * | 2014-03-12 | 2014-06-18 | 福州大学 | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst |
| CN103861632A (en) * | 2014-04-07 | 2014-06-18 | 吉林大学 | Preparation method for multi-hole carbon nitride photocatalytic material doped with sulphur |
| CN104399509A (en) * | 2014-12-08 | 2015-03-11 | 福州大学 | Hydrogen-free precursor synthesized carbon nitride photocatalyst |
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| CN109319751A (en) * | 2018-11-14 | 2019-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of mesoporous graphite phase carbon nitride being made of hollow ball and products thereof and application |
| CN112264073A (en) * | 2020-10-29 | 2021-01-26 | 电子科技大学 | Helical structure C3N4Preparation method of nanofiber photocatalyst |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003050036A1 (en) * | 2001-12-11 | 2003-06-19 | Nanomix Inc. | Increasing hydrogen adsorption of nanostructures storage materials by modifying sp2 covalent bonds |
| CN102874777A (en) * | 2012-09-28 | 2013-01-16 | 常州大学 | High-specific-surface-area mesoporous graphite-phase carbon nitride material and preparation method thereof |
-
2013
- 2013-05-13 CN CN201310174297.9A patent/CN103240119B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003050036A1 (en) * | 2001-12-11 | 2003-06-19 | Nanomix Inc. | Increasing hydrogen adsorption of nanostructures storage materials by modifying sp2 covalent bonds |
| CN102874777A (en) * | 2012-09-28 | 2013-01-16 | 常州大学 | High-specific-surface-area mesoporous graphite-phase carbon nitride material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CRISTIANO GERALDO DE FARIA等: "Conformational Analysis and Electronic Structure of Chiral Carbon and Carbon Nitride Nanotubes", 《MATERIALS RESEARCH》 * |
| HAIYING JIN: "Mesoporous Silicas by Self-Assembly of Lipid Molecules: Ribbon,Hollow Sphere,and Chiral Materials", 《CHEM.EUR.J.》 * |
| 檀波等: "介孔类石墨氮化碳的制备及其催化Knoevenagel 缩合反应", 《化学通报》 * |
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