CN107335460A - A kind of preparation method and applications of composite photocatalyst material - Google Patents
A kind of preparation method and applications of composite photocatalyst material Download PDFInfo
- Publication number
- CN107335460A CN107335460A CN201710605248.4A CN201710605248A CN107335460A CN 107335460 A CN107335460 A CN 107335460A CN 201710605248 A CN201710605248 A CN 201710605248A CN 107335460 A CN107335460 A CN 107335460A
- Authority
- CN
- China
- Prior art keywords
- agnps
- preparation
- solution
- methanol
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 238000004108 freeze drying Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 86
- 239000000243 solution Substances 0.000 description 54
- 239000003054 catalyst Substances 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000000499 gel Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZXNYKOAICSPUKI-UHFFFAOYSA-N dicyanocyanamide Chemical compound N#CN(C#N)C#N ZXNYKOAICSPUKI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/58—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
Abstract
A kind of preparation method and applications of composite photocatalyst material, belong to photocatalysis field.By processes such as freeze-drying, Hydrothermal Synthesiss and high-temperature calcinations, finally give to AgNPs/g C visible light-responded, that activated centre is more, absorptivity and photocatalytic activity are higher3N4Composite photocatalyst material.The preparation process of the composite is simple, reaction condition is gentle, and raw material are relatively inexpensive, be easy to get, toxicity is low and environmentally friendly.The AgNPs/g C of preparation3N4Composite photocatalyst material at room temperature can catalysis methanol dehydrogenation be made hydrogen, provide certain reference for the industrialized utilization of absolute methanol.
Description
Technical field
The invention belongs to environmental chemical engineering photocatalysis technology field, and in particular to the production technical field of photochemical catalyst.
Background technology
Fossil fuel traditional at present can not adapt to efficient today's society, economy, cleaning energy to the seriously polluted of environment
The standard of source system, while the getting worse of global environmental problem, also people are caused more to pay attention to utilization and the environment of the energy
Protection.Hydrogen Energy is one of preferable clean energy resource, is all widely used in many aspects as important industrial chemicals.
Methanol is a kind of important industrial chemicals, both can chemically be synthesized from fossil resource, again can be from biomass system
Taking, molecular structure is simple, using methanol direct dehydrogenation is to study more scheme at present under anaerobic and various catalysts conditions,
Wherein select the key point that excellent catalyst is this method research.There is the catalysis of many methanol direct dehydrogenations at present
Agent, metal, zeolite, carbonate and the class of oxide four can be divided into according to the difference of its property, but because a variety of causes is all without real
Now industrialize.
g-C3N4Possess visible light-responded ability and high stability, available for Methanol Decomposition, water decomposition, dyestuff degraded etc.
Aspect.But g-C3N4There is also many limitations, for example band gap is narrower, the combination speed of electron hole pair, limitation
The development in its field in photocatalysis.
The content of the invention
For problem above existing for prior art, the present invention is intended to provide a kind of synthesis being simple to operate and friendly to environment
Method, the photochemical catalyst of preparation can have good photocatalysis performance catalysis methanol hydrogen manufacturing under visible light.
The present invention comprises the following steps：
1）By dicyanodiamine（CGN）It is dissolved in water, obtains nitrogen source solution；
2）Stood after silver nitrate solution is mixed with nitrogen source solution, in-situ preparation Ag/CGN compounds（Gel）；
3）After Ag/CGN compounds are freeze-dried, it is placed in reactor and carries out hydro-thermal reaction, then forged again through tube furnace high temperature
Burn, obtain AgNPs/g-C3N4Composite photo-catalyst.
Dicyanodiamine of the present invention（CGN）It is under static conditions that dicyanodiamine is anti-with silver nitrate using water as solvent for nitrogen source
Should, cyanide nitrogen and imino group nitrogen in dicyanodiamine form polymer with Ag atom combinations bridging, to reach in-situ preparation gel
The purpose of shape Ag/CGN compounds, the purpose of freeze-drying are removed in by the moisture content in gel Ag/CGN compounds, obtained
Aeroge.Pass through hydro-thermal reaction and high-temperature calcination again, finally give AgNPs/g-C of the pattern for threadiness3N4Composite photocatalyst
Agent.
Because Ag compounds are unstable under visible light, Ag nano particles can be produced, it will be apparent that improve g-C3N4Light urge
Change activity.The present invention by adulterating Ag compounds solves the problems, such as that prior art is present, and the composite photo-catalyst of synthesis is can
See under optical condition, can be simple to operate and friendly to environment methanol direct dehydrogenation generation anhydrous formaldehyde and hydrogen, the hydrogen producing technology.
The present invention has the characteristics of following excellent using the assembling of molecule from bottom to top synthetic method：
1st, the raw material prepared be easy to get, advantage of lower cost, toxicity it is relatively low.
2nd, obtained catalyst efficiency is higher, g-C3N4It can continue to produce electron-hole position, stability improves.
3rd, redox characteristic gentle Ag can be selectively by methanol dehydrogenation formaldehyde and hydrogen, and without COxProduce.
4th, the preparation process of material of the present invention has that reaction condition is gentle, method easy the characteristics of being easy to get.
Further, step 2 of the present invention）In, silver nitrate and dicyanodiamine in nitrogen source solution in silver nitrate solution
Molar ratio is 1: 15~30.Silver nitrate solution and dicyanodiamine solution in this mol ratio can fully react, generation
Stable hydrogel.
The concentration of dicyanodiamine is 0.5~3mol/L in the nitrogen source solution, and silver nitrate is dense in the silver nitrate solution
Spend for 0.1~1mol/L.It can fully be reacted in the silver nitrate solution and dicyanodiamine solution of concentration, generate stable water-setting
Glue, excessive concentration waste reagent, and the hydrogel of the too low generation of concentration is unstable, and final pattern is not molded.
The temperature conditionss of the hydro-thermal reaction are 80~200 DEG C, and the reaction time is 2~12h.The temperature of the high-temperature calcination
Condition is 300~650 DEG C, and the time is 1~10h.The purpose of this temperature and time scope is that CGN can be formed by polycondensation
Triazine ring tripolymer, further forms high-molecular compound, and last polycondensation is the g-C of graphite laminate structure3N4, less than this temperature
Degree can not form g-C3N4, will be decomposed higher than this temperature range, the excessive velocities meeting of heating and calcination time influence
Final AgNPs/g-C3N4The pattern of compound, the pattern of the catalyst formed in this temperature range is filamentary structure.
The present invention is another object is that propose AgNPs/g-C made from above method3N4Composite photo-catalyst is aoxidized in methanol and made
Application in hydrogen.
In 2~20 DEG C of environment, by AgNPs/g-C3N4After composite photo-catalyst and methanol mixing, under oxygen free condition, Yu Bo
Length >=420nm radiation of visible light, is reacted, and hydrogen is made.
Through testing obtained hydrogen, wherein not carbonated.
The AgNPs/g-C prepared from the inventive method3N4Compared to other catalyst, methanol can be decomposed at room temperature
Produce hydrogen, and without COx produce, without the stringent condition of HTHP, economize on resources, catalyst performance stabilised can continuously produce hydrogen and
Formaldehyde, the reference value of preciousness is provided for industrialized production formaldehyde.
Brief description of the drawings
Fig. 1 is the infrared contrast spectrogram of pure CGN and Ag/CGN compounds（FT-IR）.
Fig. 2 is AgNPs/g-C3N4Compound and AgNO3Ag3d high powers XPS contrast collection of illustrative plates.
Fig. 3 is that the SEM of Ag/CGN aeroges schemes.
Fig. 4 is that the SEM of AgNPs/g-C3N4 composite photo-catalysts schemes.
Fig. 5 is AgNPs/g-C3N4Specific surface area test chart（BET）.
Fig. 6 is AgNPs/g-C3N4And g-C3N4X-ray diffracting spectrum（XRD）.
Fig. 7 is AgNPs/g-C3N4And g-C3N4Infrared contrast spectrogram.
Fig. 8 is AgNPs/g-C3N4And g-C3N4The full spectrograms of XPS.
Fig. 9 is AgNPs/g-C3N4Ag3d high-resolution XPS spectrum figures.
Figure 10 is AgNPs/g-C3N4And g-C3N4High-resolution C1s XPS spectrum figures.
Figure 11 is AgNPs/g-C3N4High-resolution-ration transmission electric-lens figure（HR-TEM）.
Figure 12 is AgNPs/g-C3N4Details in a play not acted out on stage, but told through dialogues high-resolution-ration transmission electric-lens figure.
Figure 13 is AgNPs/g-C3N4And g-C3N4UV-Vis DRS collection of illustrative plates.
Figure 14 is AgNPs/g-C3N4And g-C3N4Fluorescence spectrophotometer spectrogram（PL）.
Figure 15 is AgNPs/g-C at room temperature3N4And g-C3N4Decompose the schematic diagram of methanol production hydrogen.
Figure 16 is AgNPs/g-C3N4Photocatalysis methanol produces the mechanism figure of hydrogen and formaldehyde.
Figure 17 is that phenol reagent method is determined after light-catalyzed reaction, the analysis chart of content of formaldehyde in methanol.
Figure 18 is different light application times, and formaldehyde is generated in methanol contains spirogram.
Embodiment
Embodiment 1：
1st, by analytically pure AgNO3Dissolving in deionized water, is configured to the clear solution that concentration is 0.1mol/L, resulting solution
It is designated as solution A.
2nd, CGN is added in deionized water, is configured to the clear solution that concentration is 0.5mol/L, resulting solution is to be designated as
Solution B.
3rd, 1mL solution As are added in 6mL solution Bs, stood after mixing, eventually form milk white gel shape Ag/CGN
Compound.
4th, reactor hydro-thermal reaction after gel refrigeration drying obtained above, will be put into, reaction temperature is 80 DEG C and maintained
2h, then tube furnace high-temperature calcination, condition are that 10 DEG C/min is raised to 300 DEG C and maintains 3h, are finally cooled to room temperature, finally give
AgNPs/g-C3N4Composite photo-catalyst.
Embodiment 2：
1st, by analytically pure AgNO3Dissolving in deionized water, is configured to the clear solution that concentration is 0.2mol/L, resulting solution
It is designated as solution A.
2nd, dicyanodiamine is added in deionized water, is configured to the clear solution that concentration is 0.8mol/L, resulting solution
To be designated as solution B.
3rd, 2mL solution As are added in 10mL solution Bs, stood after mixing, eventually formed milk white gel shape Ag/CGN and answer
Compound.
4th, reactor hydro-thermal reaction after gel refrigeration drying obtained above, will be put into, reaction temperature is 150 DEG C and maintained
5h, then tube furnace high-temperature calcination, condition are that 15 DEG C/min is raised to 400 DEG C and maintains 5h, are finally cooled to room temperature, finally give
AgNPs/g-C3N4Composite photo-catalyst.
Embodiment 3
1st, by analytically pure AgNO3Dissolving in deionized water, is configured to the clear solution that concentration is 1mol/L, resulting solution note
For solution A.
2nd, CGN is added in deionized water, is configured to the clear solution that concentration is 3mol/L, resulting solution is molten to be designated as
Liquid B.
3rd, 5mL solution As are added in 15mL solution Bs, stood after mixing, eventually form gel.
4th, reactor hydro-thermal reaction after gel refrigeration drying obtained above, will be put into, reaction temperature is 200 DEG C and maintained
10h, then tube furnace high-temperature calcination, condition are that 20 DEG C/min is raised to 650 DEG C and maintains 8h, are finally cooled to room temperature, final to obtain
To AgNPs/g-C3N4Composite photo-catalyst.
2nd, product property is verified：
Take CGN and AgNPs/g-C3N4Composite photo-catalyst sample obtains infrared spectrum (FT-IR) respectively, as shown in figure 1, can
See：Compared with pure CGN, due to the AgNPs/g-C of formation3N4NO in composite photo-catalyst be present3 —, so composite photo-catalyst exists
1385cm-1There is obvious peak at place.
Take analytically pure AgNO3Ag3d XPS spectrum figure is obtained respectively with the Ag/CGN compounds of preparation, as shown in Fig. 2 can
See：With AgNO3Compare, Ag3d peak combines energy direction displacement toward high in Ag/CGN compounds, can mainly due to Ag atoms
Induce the electronics in cyanide nitrogen and imino group nitrogen.
Fig. 3 shows the SEM figures of Ag/CGN aeroges, it is seen that：The pattern of Ag/CGN aeroges is fibrous, the length of fiber
Degree is up to some tens of pm.
Fig. 4 then shows the AgNPs/g-C3N4 complex lights for obtaining Ag/CGN aeroges by hydro-thermal reaction and high-temperature calcination
The SEM figures of catalyst, it is seen that：The pattern of catalyst is still in threadiness, but these fibers are connected to become network structure.
Take AgNPs/g-C3N4Composite photo-catalyst sample carries out specific surface area test, obtains BET figures as shown in Figure 5, can
See：AgNPs/g-C3N4The specific surface area of composite photo-catalyst is 139 m2/ g, compare g-C3N4Specific surface area (8-12 m2/g)
It is high at least 10 times, illustrate AgNPs/g-C3N4With higher N2 adsorption ability.
Fig. 6 is AgNPs/g-C3N4And g-C3N4X-ray diffraction contrast collection of illustrative plates (XRD).g-C3N413.3 oWith 27.3oThere are two peaks at place, and 27.3oPeak be due to the stacking stacking for being conjugated aroma system, be layer structure, 13.3 oFor g-C3N4Face
Inner structure, (100) face and (002) face are corresponded to respectively；And AgNPs/g-C3N4There is AgNPs and g-C simultaneously3N4Diffraction
Peak, but（002）Face peak width and weak, it may be possible to because in polymer process is formed, C/N ratios are changed, and cause product to contract
Poly- degree is different, and then causes g-C3N4The interlamellar spacing of layer structure becomes big.37o-80 oThere is peak at place, illustrates that AgNPs in-situ preparations exist
G-C3N4Face-centered cubic crystal face (JCPDS 65-2871) in.
Fig. 7 is AgNPs/g-C3N4And g-C3N4Infrared contrast spectrogram.1700-1100cm-1Between absorption high-amplitude wave section master
If due to CN stretching vibration, ~ 800cm-1The peak at place corresponds to 3-s- triazine ring structures, this mutual in order to further confirm that
Effect, XPS are used for confirming AgNPs/g-C3N4And g-C3N4Between chemical component and bond structure between difference.
Fig. 8 is AgNPs/g-C3N4And g-C3N4XPS compose comparison diagram entirely.C, N, Ag elemental signals can be in AgNPs/g-
C3N4Middle discovery, illustrate that reaction forms AgNPs/g-C3N4。
Fig. 9 is AgNPs/g-C3N4Ag3d high-resolution XPS spectrum figures.In Ag3d high-resolution XPS collection of illustrative plates, Ag3d3/2With
Ag3d5/2The combination of two characteristic peaks can be respectively 374.3 and 368.3eV, compared with Ag/CGN peak（374.5eV and
368.8eV）About 0.5eV is reduced, illustrates the formation of argent.
Figure 10 is AgNPs/g-C3N4C1s high-resolution XPS contrast spectrogram.Due to the thermal degradation of nitrate in Ag/CGN,
AgNPs/g-C3N4C-O peak areas（286.6eV）Than g-C3N4Height.
From Figure 11 AgNPs/g-C3N4High-resolution-ration transmission electric-lens figure (HR-TEM) it can be seen that prepare AgNPs/g-
C3N4Pattern for threadiness.From Figure 12 AgNPs/g-C3N4Details in a play not acted out on stage, but told through dialogues high-resolution-ration transmission electric-lens figure to can see AgNPs uniform
Be dispersed in g-C3N4In matrix.
From Figure 13 AgNPs/g-C3N4And g-C3N4UV-Vis DRS collection of illustrative plates can see, AgNPs/g-C3N4
Absorption band edge wavelength more than 800nm, and absorption intensity compares g-C between 200~800nm3N4It is strong a lot, mainly
The reason for AgNPs formation.
From Figure 14 AgNPs/g-C3N4And g-C3N4Fluorescence spectrophotometer spectrogram（PL）It can analyze：AgNPs/g-C3N4It is glimmering
Luminous intensity and g-C3N4Compared to it is weak a lot, illustrate that AgNPs doping causes g-C3N4Fluorescence be quenched, it is photic swash
It is unfavorable for the combination of electron-hole during hair.The separation and transfer of electronics are attributed to AgNPs/g-C3N4And 3-D nano, structure
And Ag characteristic, be advantageous to attract electronics and by electronics from g-C3N4Interior shifting to surface.
Above AgNPs/g-C3N4Composite photo-catalyst sample may be derived from the product of any one in three above embodiment,
The result of acquirement is similar.
3rd, apply：
Application examples 1：
By 30mL methanol, AgNPs/g-C made from the method for 5mg embodiments 13N4Composite photo-catalyst is added to quartz reactor
In, solution is placed in after persistently stirring in 6 DEG C of circulator bath, and air in reactor is pumped, with xenon lamp in wavelength >=420nm
Under the conditions of irradiate solution 3h, you can by Methanol Decomposition, formaldehyde and hydrogen, the hydrogen that TCD detections obtain is made.
Separately by 30mL methanol, 5mg g-C3N4It is added in quartz reactor, 6 DEG C of circulator bath is placed in after lasting stirring
In, air in reactor is pumped, after irradiating solution 3h under the conditions of wavelength >=420nm with xenon lamp, the hydrogen of TCD tests acquirement
Gas.
The content of production hydrogen is surveyed according to TCD, Figure 15 AgNPs/g-C is made3N4And g-C3N4Decompose the contrast of methanol production hydrogen
Figure.As shown in Figure 15, g-C at room temperature3N4Methanol production hydrogen, and AgNPs/g-C can not be decomposed3N4The production hydrogen of composite photo-catalyst
Speed is 152.2 μm of ol/h/g, gradually increases by circulating hydrogen-producing speed three times, illustrates AgNPs/g-C3N4Composite photo-catalyst
It is stable in methanol decomposition process, and catalysis methanol production hydrogen can be continued.
CO、CO2Calibrating gas is detected with caused gas by fid detector, by comparing, AgNPs/g-C3N4Catalyst
By in gas caused by photocatalysis methanol without CO and CO2Generation.Illustrate at room temperature, AgNPs/g-C3N4Composite photo-catalyst
Methanol production hydrogen, and no coupling product CO can be decomposedXProduce.
It was found from the mechanism of Figure 16 photocatalysis methanol degradations, g-C3N4Produce photohole and be transferred to AgNPs/g-C3N4
Catalyst and methanol surface, promote CH3OH produces CH2OH, CH2OH and Ag generations Ag-OCH3, Ag-OCH3It is readily generated
Ag-H and HCHO, caused Ag-H easily and proton H+Pass through e-Generate H2.Due to redox characteristic gentle Ag and low anti-
Temperature is answered, caused HCHO can not be aoxidized further under vacuo, while avoid COx generation.
Content of formaldehyde after photocatalysis in methanol is determined by phenol reagent method：Gradient draws formaldehyde standard respectively
The mL of liquid (0.1mg/L) 0,0.1,0.5,1.0,2.0,3.0 is in 6 volumetric flasks, another each methanol drawn after 1mL photocatalysis
Solution in 2 volumetric flasks, adds 0.1mL phenol reagent solution respectively into above-mentioned 8 volumetric flasks respectively with the pure methanol solutions of 1mL,
Shake up, stand 1min, then be separately added into 0.1mL sulfuric acid acid iron ammonium salt solution, be settled to scale, shake up, after 10min colour developings, with
Blank does reference, and absorbance is surveyed at 300nm wavelength, draws standard curve Figure 17, calculates the content of formaldehyde in solution after reacting.
And obtain the analysis chart of content of formaldehyde in Figure 18 methanol.As seen from Figure 18：Increase over time, contained formaldehyde in methanol
Content gradually increases, and illustrates at room temperature, AgNPs/g-C3N4Methanol dehydrogenation anhydrous formaldehyde can be decomposed.
Application examples 2：
By 50mL methanol, AgNPs/g-C made from the method for 25mg examples 23N4Composite photo-catalyst is added in quartz reactor,
It is placed in after lasting stirring in 10 DEG C of circulator bath, after air in reactor is pumped, with xenon lamp in wavelength >=420nm conditions
Lower irradiation mixed solution 6h, you can by Methanol Decomposition, formaldehyde and hydrogen is made.
Caused gas H2Detected by gas-chromatography TCD detectors, through fid detector detect caused by gas without CO
And CO2, illustrate at room temperature, AgNPs/g-C3N4Composite photo-catalyst can decompose methanol production hydrogen, and no coupling product COXProduce.
Content of formaldehyde after photocatalysis in methanol solution is determined by phenol reagent method.
Gradient draws formaldehyde titer (1mg/L) 0,0.2,0.6,0.8,1.0,3.0 mL in 6 volumetric flasks respectively,
Solution after another each absorption 3mL photocatalysis in 2 volumetric flasks, divides into above-mentioned 8 volumetric flasks respectively with the pure methanol solutions of 3mL
Not plus 1mL phenol reagent solution, shake up, stand 5min, then be separately added into 2mL sulfuric acid acid iron ammonium salt solution, be settled to scale, shake
It is even, after 15min colour developings, reference is done with blank, absorbance is surveyed in 400 nanometer wave strong points, draws standard curve, is calculated molten after reacting
The content of formaldehyde in liquid.
Application examples 3：
By 60mL methanol, AgNPs/g-C made from 50mg embodiments 33N4Composite photo-catalyst is added in quartz reactor, is held
It is placed in after continuous stirring in 20 DEG C of circulator bath, after air in reactor is pumped, with xenon lamp under the conditions of wavelength >=420nm
Irradiate mixed solution 8h, you can by Methanol Decomposition, formaldehyde and hydrogen is made.
Caused gas H2Detected by gas-chromatography TCD detectors, through fid detector detect caused by gas without CO
And CO2, illustrate at room temperature, AgNPs/g-C3N4Composite photo-catalyst can decompose methanol production hydrogen, and no coupling product COXProduce.
Content of formaldehyde after photocatalysis in methanol solution is determined by phenol reagent method.
Gradient draws formaldehyde titer (5mg/L) 0,0.5,1.0,3.0,5.0,8.0 mL in 6 volumetric flasks respectively,
Methanol solution and the pure methanol solutions of 5mL after another each absorption 5mL photocatalysis is in 2 volumetric flasks, respectively to above-mentioned 8 volumetric flasks
It is middle to add 3mL phenol reagent solution respectively, shake up, stand 10min, then 4mL sulfuric acid acid iron ammonium salt solution is separately added into, it is settled to quarter
Degree, is shaken up, and after 20min colour developings, reference is done with blank, absorbance is surveyed at 600nm wavelength, draws standard curve Figure 17, is calculated
After illumination in solution formaldehyde content, as shown in Figure 18, after reaction in solution（Figure 15 circulate three times after solution）Formaldehyde contains
Measure as 0.305mg/L, the content of formaldehyde is 0.054 mg/L in 2h solution after illumination, and the content of formaldehyde is in 2h solution after illumination
0.070 mg/L, the content for thus illustrating to be converted into formaldehyde with the increase of light application time, methanol gradually increase, but and hydrogen output
Compared to many less, because reaction is to carry out under vacuum and formaldehyde is volatile.
In a word, AgNPs/g-C has been synthesized by the inventive method in-situ synthesized3N4, with g-C3N4Compared to not only changing
g-C3N4Structure and performance, and AgNPs/g-C3N4Structure and photocatalysis performance with uniqueness, can be decomposed at room temperature
Methanol dehydrogenation formaldehyde and hydrogen, and no coupling product COXProduce, provide for industrialized production formaldehyde and production hydrogen and refer to sexual valence
Value.
Claims (7)
1. a kind of preparation method of composite photocatalyst material, it is characterised in that comprise the following steps：
1）Dicyanodiamine is dissolved in water, obtains nitrogen source solution；
2）Stood after silver nitrate solution is mixed with nitrogen source solution, in-situ preparation Ag/CGN compounds；
3）After Ag/CGN compounds are freeze-dried, it is placed in reactor and carries out hydro-thermal reaction, then forged again through tube furnace high temperature
Burn, obtain AgNPs/g-C3N4Composite photo-catalyst.
2. preparation method according to claim 1, it is characterised in that the step 2）In, in silver nitrate solution silver nitrate with
The molar ratio of dicyanodiamine is 1: 15~30 in nitrogen source solution.
3. preparation method according to claim 1 or 2, it is characterised in that the concentration of dicyanodiamine is in the nitrogen source solution
0.5~3mol/L.
4. preparation method according to claim 1 or 2, it is characterised in that the concentration of silver nitrate is in the silver nitrate solution
0.1~1mol/L.
5. preparation method according to claim 1, it is characterised in that the temperature conditionss of the hydro-thermal reaction are 80~200
DEG C, the reaction time is 2~10h.
6. preparation method according to claim 1, it is characterised in that the temperature conditionss of the high-temperature calcination are 300~650
DEG C, the time is 3~8h.
7. the AgNPs/g-C as made from claim 1 method3N4Application of the composite photo-catalyst in methanol aoxidizes hydrogen manufacturing, it is special
Sign is：In 2~20 DEG C of environment, by AgNPs/g-C3N4After composite photo-catalyst and methanol mixing, under oxygen free condition, Yu Bo
Length >=420nm radiation of visible light, is reacted, and hydrogen is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710605248.4A CN107335460B (en) | 2017-07-24 | 2017-07-24 | A kind of preparation method and applications of composite photocatalyst material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710605248.4A CN107335460B (en) | 2017-07-24 | 2017-07-24 | A kind of preparation method and applications of composite photocatalyst material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107335460A true CN107335460A (en) | 2017-11-10 |
| CN107335460B CN107335460B (en) | 2019-11-01 |
Family
ID=60216465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710605248.4A Active CN107335460B (en) | 2017-07-24 | 2017-07-24 | A kind of preparation method and applications of composite photocatalyst material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107335460B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108714431A (en) * | 2018-03-22 | 2018-10-30 | 中南林业科技大学 | A kind of nano-cellulose enhancing composite photo-catalyst and its preparation method and application |
| CN112675843A (en) * | 2021-01-11 | 2021-04-20 | 西部金属材料股份有限公司 | Silver quantum dot composite photocatalyst and preparation method thereof |
| CN113831349A (en) * | 2021-08-20 | 2021-12-24 | 厦门大学 | Preparation method of urotropine |
| CN114360922A (en) * | 2022-01-17 | 2022-04-15 | 南京信息工程大学 | Ag/g-C3N4Composite material and electrode material prepared from same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475140A (en) * | 2014-11-07 | 2015-04-01 | 江苏大学 | Silver-modified carbon nitride composite photocatalytic material and preparation method thereof |
| CN105214700A (en) * | 2015-09-21 | 2016-01-06 | 天津工业大学 | Silver orthophosphate/g-C 3n 4composite membrane and synthetic method thereof |
| CN105457658A (en) * | 2015-12-08 | 2016-04-06 | 哈尔滨工业大学深圳研究生院 | Z-type catalyst capable of simulating photosynthesis to degrade pollutants and generate hydrogen simultaneously, and preparation method of Z-type catalyst |
| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
-
2017
- 2017-07-24 CN CN201710605248.4A patent/CN107335460B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475140A (en) * | 2014-11-07 | 2015-04-01 | 江苏大学 | Silver-modified carbon nitride composite photocatalytic material and preparation method thereof |
| CN105214700A (en) * | 2015-09-21 | 2016-01-06 | 天津工业大学 | Silver orthophosphate/g-C 3n 4composite membrane and synthetic method thereof |
| CN105457658A (en) * | 2015-12-08 | 2016-04-06 | 哈尔滨工业大学深圳研究生院 | Z-type catalyst capable of simulating photosynthesis to degrade pollutants and generate hydrogen simultaneously, and preparation method of Z-type catalyst |
| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
Non-Patent Citations (1)
| Title |
|---|
| QING HAN ET AL.: "A Graphitic-C3N4 "Seaweed" Architecture for Enhanced Hydrogen Evolution", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108714431A (en) * | 2018-03-22 | 2018-10-30 | 中南林业科技大学 | A kind of nano-cellulose enhancing composite photo-catalyst and its preparation method and application |
| CN108714431B (en) * | 2018-03-22 | 2021-03-16 | 中南林业科技大学 | Nano-cellulose reinforced composite photocatalyst and preparation method and application thereof |
| CN112675843A (en) * | 2021-01-11 | 2021-04-20 | 西部金属材料股份有限公司 | Silver quantum dot composite photocatalyst and preparation method thereof |
| CN113831349A (en) * | 2021-08-20 | 2021-12-24 | 厦门大学 | Preparation method of urotropine |
| CN114360922A (en) * | 2022-01-17 | 2022-04-15 | 南京信息工程大学 | Ag/g-C3N4Composite material and electrode material prepared from same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107335460B (en) | 2019-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107335460B (en) | A kind of preparation method and applications of composite photocatalyst material | |
| Wang et al. | 0D/2D heterojunctions of Ti3C2 MXene QDs/SiC as an efficient and robust photocatalyst for boosting the visible photocatalytic NO pollutant removal ability | |
| Sun et al. | Template-free self-assembly of three-dimensional porous graphitic carbon nitride nanovesicles with size-dependent photocatalytic activity for hydrogen evolution | |
| CN106076421B (en) | A kind of MIL-53 (Fe)/g-C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| Wang et al. | Novel polypyrrole-sensitized hollow TiO2/fly ash cenospheres: Synthesis, characterization, and photocatalytic ability under visible light | |
| CN103143338B (en) | Porous titanium dioxide/graphene composite material and preparation method thereof | |
| CN100396373C (en) | Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst | |
| CN103480353A (en) | Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst | |
| CN108620131B (en) | In-situ preparation method of composite photocatalytic material | |
| CN104888837A (en) | Synthetic method and application of visible-light responding carbon nitride/iron sesquioxide nano composite | |
| CN108686665B (en) | Preparation method of nanorod zinc ferrite in-situ composite lamellar titanium dioxide photocatalytic material | |
| CN104923276B (en) | A kind of preparation method of the compound nickel ferrite based magnetic loaded magnetic photocatalytic material of graphite type carbon nitride | |
| CN109999887B (en) | beta-FeOOH/g-C3N4Preparation method of heterojunction photocatalytic material | |
| CN112718009B (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
| CN109692701A (en) | g-C3N4/MoS2Composite photo-catalyst and its one-pot preparation thereof | |
| CN103990472A (en) | Stable and efficient hydrogen production co-catalyst and preparation method thereof | |
| Yang et al. | In situ self-assembly synthesis of carbon self-doped graphite carbon nitride hexagonal tubes with enhanced photocatalytic hydrogen evolution | |
| CN105562093A (en) | Photocatalyst and preparation method thereof, catalyst for hydrogen production from photocatalytic decomposition and preparation method thereof, and preparation method of hydrogen | |
| Zhao et al. | Fabrication of novel BiPO4/Bi4O5Br2 heterojunctions for improving photoactivity in N2 fixation and dye degradation | |
| Ren et al. | One-pot fabrication of porous nitrogen-deficient g-C3N4 with superior photocatalytic performance | |
| Paul et al. | Mg/Li@ GCN as highly active visible light responding 2D photocatalyst for wastewater remediation application | |
| Su et al. | Creating distortion in g-C3N4 framework by incorporation of ethylenediaminetetramethylene for enhancing photocatalytic generation of hydrogen | |
| CN114591477B (en) | Preparation and application of imine-linked dibenzothiophene sulfonyl covalent organic framework material | |
| Sun et al. | Covalent triazine frameworks (CTFs) for photocatalytic applications | |
| Yan et al. | Hydroxyl-rich porous silica nanosheets decorated with oxygen-doped carbon nitride nanoparticles for photocatalytic degradation of rhodamine B |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |