CN107744824A - A kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application - Google Patents
A kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application Download PDFInfo
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- CN107744824A CN107744824A CN201710255730.XA CN201710255730A CN107744824A CN 107744824 A CN107744824 A CN 107744824A CN 201710255730 A CN201710255730 A CN 201710255730A CN 107744824 A CN107744824 A CN 107744824A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 230000009467 reduction Effects 0.000 claims abstract description 42
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims abstract description 16
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 29
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 20
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 16
- 238000010304 firing Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000003138 coordinated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of g C of modification3N4Base visible-light photocatalyst, its preparation method and application, its object is to by using NaBH4The method of reduction is to g C3N4Base is modified, and changes its band gap width and position, so as to increase its response range to visible ray, and by changing its valence band and conduction band positions, so as to can photochemical catalytic oxidation water, reduction oxygen in water production hydrogen peroxide, thus solve prior art to g C3N4Although its photocatalysis performance still cost height, and can not fundamentally change the low technical problem of its visible light utilization efficiency can be improved by being modified.
Description
Technical field
The present invention relates to field of photocatalytic material, more particularly to g-C3N4Modified g-C3N4Based photocatalyst and system
Preparation Method.
Background technology
β-C are theoretically proposed from the Liu and Cohen of University of California in 19893N4Since covalent crystal, be carbonized nitrification
Thing therefore the extensive concern in photocatalysis field by scientists from all over the world, A.Y.Liu and M.L.Cohen is according to β-Si within 19893N4
Crystal structure, with C replace Si, under local density of state approximation using primary pseudo potential can band method theoretically foretell β-
C3N4(i.e. carbonitride) this hardness can compare favourably with diamond and be the still undiscovered new covalent combination in nature
Thing.1996, Teter and Hemley thought C by calculating3N4May have 5 kinds of structures, i.e. α phases, β phases, Emission in Cubic, standard cube
Phase and class graphite-phase, wherein graphite-phase C3N4It is C under normal temperature3N4In most stable of phase, while material non-toxic, and having visible
Photoresponse, therefore be widely used in photocatalysis.In addition C3N4Prepare it is simple, cheap, become without metal
A kind of novel photocatalyst.
But g-C3N4(graphite-phase nitrogen carbide) is there is also some shortcomings, for example photo-generate electron-hole recombination rate is high and cause
Photo-quantum efficiency it is low, the problems such as oxidability is low and photohole mobility is low.G-C simultaneously3N4Band gap is 2.7eV, although
With good visible light-responded property, but valence band is located at+1.4V (vs.Ag/AgCl, pH=6.6), it is difficult to aoxidizes water, seriously
Limit g-C3N4Development and application.
With going deep into for research, there are many scholars to employ a variety of methods now and come to g-C3N4It is modified, such as：
Compound and other semiconductors couplings etc. are carried out with precious metal material, although the addition of precious metal material makes g-C3N4Show more
Good photocatalysis performance, but the cost of catalyst is also considerably increased simultaneously, limit g-C3N4Application, and can not be from
Fundamentally change low visible light utilization efficiency.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of g-C of modification3N4Base visible ray
Photochemical catalyst, its preparation method and application, its object is to by using NaBH4The method of reduction is to g-C3N4Base is modified,
Change its band gap width and position, so as to increase its response range to visible ray, and by changing its valence band and conduction band positions,
So as to can photochemical catalytic oxidation water, reduction oxygen in water production hydrogen peroxide, thus solve prior art to g-C3N4Changed
Although property can improve its photocatalysis performance but cost is high, and can not fundamentally change the low technology of its visible light utilization efficiency
Problem.
To achieve the above object, according to one aspect of the present invention, there is provided a kind of g-C of modification3N4Base visible ray light is urged
Agent, the direct band gap width of the photochemical catalyst is 2.4~2.7eV, indirect band gap width is 1.7~2.65eV.
Preferably, the photochemical catalyst directly absorbing wavelength can be 550nm visible ray, and can absorb indirectly whole
The visible ray of visible region.
Preferably, C ≡ N are included in the photocatalyst elements structure, its infrared spectrum is in 2180cm-1Position occur
C ≡ N peak.
According to another aspect of the present invention, there is provided a kind of g-C of described modification3N4Base visible-light photocatalyst
Preparation method, comprise the following steps：
(1) substance A is fired into 3~5 hours under the conditions of 400 DEG C~500 DEG C, presoma g-C is obtained after washing3N4；Institute
The g-C of three s-triazine structures can be produced after 400 DEG C~500 DEG C polymerizations by stating substance A3N4；
(2) by step (1) obtained by presoma g-C3N4Mix with reducing agent, reduce under an inert atmosphere, after washing
Obtain the g-C of described modification3N4Base visible-light photocatalyst.
Preferably, the substance A is melamine or urea.
Preferably, the substance A is melamine.
Preferably, heating rate control is in 3~15 DEG C/min when step (1) fires melamine.
Preferably, step (2) described reducing agent is NaBH4Or KBH4。
Preferably, step (2) described reducing agent is NaBH4。
Preferably, step (2) the presoma g-C3N4With the NaBH4The mass ratio of mixing is 1:(2~6).
Preferably, step (2) described reduction temperature is 300 DEG C~400 DEG C.
Preferably, step (2) described reduction temperature is 350 DEG C~370 DEG C.
Preferably, step (2) described reduction temperature is 370 DEG C.
Preferably, step (2) recovery time is 20min~40min.
Preferably, step (2) recovery time is 20min~30min.
Preferably, step (2) recovery time is 30min.
Preferably, step (2) described washing times are 2~5 times.
According to another aspect of the present invention, there is provided a kind of application of described photochemical catalyst, produced applied to photocatalysis
Hydrogen peroxide.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) g-C of prior art3N4It is a kind of catalyst of three s-triazine structures, this structure is advantageous to interior peroxide bridge
Formed, promote the generation of Double electron reduction, therefore have certain specificity for reduction oxygen production hydrogen peroxide.But due to existing
The g-C of technology3N4Valence band oxidability is limited, it is impossible to aoxidizes water, therefore in the case where reaction system is water, can not typically enter
Hydrogen peroxide is produced in row photocatalysis.The present invention is to pass through NaBH4The method of reduction, change g-C3N4Band gap width and position, a side
Face adds catalyst to visible light-responded scope, and beneficial to the absorption and utilization to visible ray, still further aspect changes g-C3N4
Valence band and conduction band positions, can photochemical catalytic oxidation water, reduction oxygen in water production hydrogen peroxide.
(2) present invention is preparing g-C3N4During presoma, it is 400 DEG C~500 DEG C, preferably 450 DEG C to select preparation temperature, and
The g-C of non-550 DEG C of firings being commonly used3N4, not only substantially increase the ability that hydrogen peroxide is produced after reducing, Er Qiejie
The cost in preparation process is saved.Modified g-C in the present invention3N4The preparation of base visible-light photocatalyst is not only needed g-
C3N4Presoma is reduced, and to g-C3N4The preparation technology of presoma also requires, modified g-C in the present invention3N4Can
See that light properties of catalyst is excellent, yields of hydrogen peroxide is big, is that the two step collaborations of presoma burning process and reducing process are matched somebody with somebody
Close, the result concured.
(3) present invention is preparing g-C3N4Noble metal is not mixed during visible-light photocatalyst, material price used at the same time is low
It is honest and clean, therefore the g-C in the present invention3N4Photochemical catalyst cost is very low.Method for preparing catalyst in addition in the present invention is simple, takes
It is short, therefore it is applied to actual production and application.
(4) present invention changes g-C during catalyst is prepared by reduction3N4Structure.The change of structure has
Beneficial to the separation in electronics and hole, electronics and hole compound probability again are greatly reduced, is on the one hand improved to visible ray
Utilization ratio, on the other hand improve the yield of hydrogen peroxide in photocatalysis.
(5) g-C prepared by the present invention3N4Based photocatalyst is still a kind of organic semiconductor, and property is stable, safe nothing
Poison, heavy metal free, therefore can widely use, while the preparation condition of catalyst is 370 DEG C, it is highly stable at normal temperatures.
(6) g-C in the present invention3N4The Absorber Bandwidth of based photocatalyst can absorb visible ray close to 550nm, directly
Connect and carry out photocatalysis using solar energy, in the system of pure water, catalysis production hydrogen peroxide, realize energy storage, this is for sustainable development
Open up significant.
(7) Peracetic acid has extraordinary effect for sterilizing, but due to the explosion hazard of Peracetic acid, extremely endangers
Danger, is not easy to store and transports, while hydrogen peroxide is again easily decomposes, and these factors all limit extensively should for Peracetic acid
With the present invention can realize produces hydrogen peroxide by reaction system photocatalysis of acetic acid, and then reacts and produce Peracetic acid, reaches
Now with the current effect, therefore the present invention has boundless application prospect.
(8) g-C in the present invention3N4Visible-light photocatalyst is in practical application, porous material table can be first carried on
Face, then photocatalysis is carried out, it on the one hand can be very good to realize the separation of catalyst and reaction system, still further aspect can be reduced
The loss of catalyst, improve the recycling rate of waterused of catalyst.
Brief description of the drawings
Fig. 1 is embodiment 1g-C3N4The g-C of presoma and the modified with reduction of embodiment 13N4UV-vis abosrption spectrograms；
Fig. 2 is embodiment 1g-C3N4The reduction g-C of presoma and the modified with reduction of embodiment 13N4Band gap diagram；
Fig. 3 is embodiment 1g-C3N4The g-C of presoma and the modified with reduction of embodiment 13N4Photoluminescence spectra；
Fig. 4 is embodiment 1g-C3N4The g-C of presoma and the modified with reduction of embodiment 13N4Hydrogen peroxide in illumination 1h systems
Yield comparison；
Fig. 5 is embodiment 1g-C3N4The g-C of presoma and the modified with reduction of embodiment 13N4Scanning electron microscope diagram；
Fig. 6 is embodiment 1g-C3N4The g-C of presoma and the modified with reduction of embodiment 13N4Infared spectrum；
Fig. 7 is comparative example 1 with the g-C of 550 DEG C of firings3N4It is that presoma passes through g-C made from reduction3N4With embodiment 1 also
The modified g-C of original3N4Yields of hydrogen peroxide compares in illumination 1h systems.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
It is embodiment below：
Embodiment 1
A kind of g-C of modification3N4The preparation method of base visible-light photocatalyst, comprises the following steps：The photochemical catalyst is can
See photoresponse type g-C3N4Based photocatalyst.
(1) preparation of presoma
Melamine is put into Muffle furnace, heating rate 3 DEG C/min, burns 4h under the conditions of 450 DEG C, make melamine high temperature
Polymerization, form the semi-conducting material g-C of three s-triazine structures of greater band gap3N4, then other things in washing and drying removal system
Matter.
(2) reducing material is prepared
By the material and NaBH of gained in (1)4It is 1 according to mass ratio:It is put into after 5 mixed grindings in tube furnace, 370 DEG C of nitrogen
30min is reduced under the conditions of gas, then the material after reduction is washed 3 times, modified g-C is can be prepared by after drying3N4Base optic catalytic
Agent.
Interpretation of result is carried out to photochemical catalyst manufactured in the present embodiment：G-C mentioned below3N4Refer to the step of embodiment 1
(1) obtained g-C is fired at 450 DEG C3N4Presoma；Reduce g-C3N4Refer to that the step of embodiment 1 (1) fires what is obtained at 450 DEG C
g-C3N4The g-C for the modification that presoma obtains through step (2) reduction3N4Based photocatalyst.
(1)g-C3N4With reduction g-C manufactured in the present embodiment3N4UV-vis spectrograms
As shown in figure 1, the g-C from the 450 DEG C of firings of UV-vis spectrum it can be seen from the figure that3N4Absorption energy for visible ray
Power is significantly lower than reduction g-C3N4.It is compared from the scope to visible absorption, the g-C of 450 DEG C of firings3N4It is only capable of absorbing
Wavelength is less than 450nm light, and the present embodiment reduces g-C3N4Absorbent wavelength is 550nm, and indirect absorbing wavelength, which extends, urges
Agent is absorbed to whole visible region, therefore reduces g-C3N4It is very high for the utilization rate of visible ray.
(2)g-C3N4With the reduction g-C of the present embodiment3N4Band gap diagram
From figure 2 it can be seen that traditional g-C3N4Only direct band gap, band gap 2.8eV, as shown in Fig. 2 (a)；And go back
G-C after original3N4Do not only have direct band gap, and indirect band gap occur, direct band gap 2.65eV, indirect band gap 2eV,
Respectively as shown in Fig. 2 (b) and Fig. 2 (c)；Illustrate that the present invention by the improvement to material, on the one hand changes its band gap width, increased
The absorption to visible ray is added, on the other hand, due to the appearance of indirect band gap, has made the absorption region of visible ray wider, it is seen that light
Utilization rate is higher.
(3)g-C3N4With the reduction g-C of the present embodiment3N4Photoluminescence spectra
From photoluminescence spectra figure, it can be evident that in Fig. 3, the g-C of 450 DEG C of firings3N4Luminous intensity is very high,
Illustrate that its electronics and hole-recombination rate are very high, the electronics and hole really to play a role during light-catalyzed reaction is seldom.And reduce g-
C3N4Luminous intensity is very weak, illustrates that the combined efficiency in its electronics and hole is very low, photocatalysis efficiency is very high, is more beneficial for visible
The utilization of light.
(4)g-C3N4With the reduction g-C of the present embodiment3N4The Yield comparison of hydrogen peroxide in illumination 1h systems
That shown in Fig. 4 is the g-C of 450 DEG C of firings3N4With reduction g-C3N4The comparison of hydrogen peroxide is produced, reaction system is：
100mL deionized waters are added in 250mL beakers, then weigh 0.1g catalyst, after being stirred 2 hours under dark condition, use 300W
Xenon lamp irradiates, and is sampled every half an hour and surveys concentration of hydrogen peroxide.Can be with it is clear to see that the g-C of 450 DEG C of firings from figure3N4Production
Amount of hydrogen peroxide is very low, close to 0, and passes through catalysis 1h concentration of hydrogen peroxide after the present invention improves and has reached 170 μm of ol/L,
And this reaction is carried out under the air conditionses for body of not ventilating, illustrates that the present invention has extraordinary practicality.
(5) Fig. 5 g-C3N4The reduction g-C of (a, c) and the present embodiment3N4The scanning electron microscope diagram of (b, d)
From g-C made from embodiment 13N4With reduction g-C3N4Scanning electron microscope diagram Fig. 5 can be seen that 450 DEG C of burnings
The g-C of system3N4It is the layer structure with rough pleats surface, while the presentation of some positions of surface is cylindric, and g-C3N4Reduction
Afterwards, layer structure is broken, and is diminished, columned g-C3N4Disappear, after illustrating reduction, g-C3N4Pattern there occurs
Change.
(6)g-C3N4With the reduction g-C of the present embodiment3N4Infared spectrum
By to g-C3N4With reduction g-C3N4Infared spectrum comparative analysis, as shown in fig. 6, can significantly find,
G-C after reduction3N4In 2180cm-1Position there is new peak, this position is C ≡ N peak, illustrate reduction after, production
C ≡ N are given birth to.And C ≡ N make g-C after being formed3N4The distribution of cloud density is changed, and makes its valence band and conduction band with present
Move.Conduction band moves down into -0.9V (vs.Ag/AgCl, pH=6.6) left and right, still there is the ability of reduction oxygen production hydrogen peroxide, valency
Band moves down into+1.8V (vs.Ag/AgCl, pH=6.6) left and right, is provided with the ability of oxidation water.
Pass through above-mentioned analysis, the g-C with visible light catalysis activity of the method preparation of the present embodiment3N4Base light is urged
Agent has the ability of very strong photocatalytic activity and very high production hydrogen peroxide, and one side hydrogen peroxide itself is nontoxic, has
Very extensive application, still further aspect, Peracetic acid can be prepared by hydrogen peroxide, Peracetic acid has kills by force very much
Bacterium effect.The present invention can realize produces hydrogen peroxide by reaction system photocatalysis of acetic acid, and then reacts and produce Peracetic acid, real
Now Peracetic acid is now with the current.
Embodiment 2
A kind of g-C of modification3N4The preparation method of base visible-light photocatalyst, comprises the following steps：The photochemical catalyst is can
See photoresponse type g-C3N4Based photocatalyst.
(1) preparation of presoma
Melamine is put into Muffle furnace, heating rate 15 DEG C/min, burns 4h under the conditions of 400 DEG C, make melamine height
Temperature polymerization, form the semi-conducting material g-C of greater band gap3N4, then other materials in washing and drying removal system.
(2) reducing material is prepared
By the material and NaBH of gained in (1)4It is 1 according to mass ratio:It is put into after 2 mixed grindings in tube furnace, 400 DEG C of nitrogen
40min is reduced under the conditions of gas, then the material after reduction is washed 3 times, modified g-C is can be prepared by after drying3N4Base optic catalytic
Agent.
Embodiment 3
A kind of g-C of modification3N4The preparation method of base visible-light photocatalyst, comprises the following steps：The photochemical catalyst is can
See photoresponse type g-C3N4Based photocatalyst.
(1) preparation of presoma
Melamine is put into Muffle furnace, heating rate 5 DEG C/min, burns 4h under the conditions of 500 DEG C, make melamine high temperature
Polymerization, form the semi-conducting material g-C of greater band gap3N4, then other materials in washing and drying removal system.
(2) reducing material is prepared
By the material and NaBH of gained in (1)4It is 1 according to mass ratio:It is put into after 6 mixed grindings in tube furnace, 300 DEG C of nitrogen
Reductase 12 0min under the conditions of gas, then the material after reduction is washed 3 times, it can be prepared by modified g-C after drying3N4Base optic catalytic
Agent.
Comparative example 1
The g-C with 550 DEG C of firings of prior art3N4Obtained g-C after being reduced for presoma3N4Preparation method, including such as
Lower step：
(1) preparation of presoma
Melamine is put into Muffle furnace, heating rate 3 DEG C/min, burns 4h under the conditions of 550 DEG C, make melamine high temperature
Polymerization, form the semi-conducting material g-C of three s-triazine structures of greater band gap3N4, then other things in washing and drying removal system
Matter.
(2) reducing material is prepared
By the material and NaBH of gained in (1)4It is 1 according to mass ratio:It is put into after 5 mixed grindings in tube furnace, 370 DEG C of nitrogen
30min is reduced under the conditions of gas, then the material after reduction is washed 3 times, the g-C being modified under the conditions of this is can be prepared by after drying3N4Base
Photochemical catalyst.
By comparative example 1 with the g-C of 550 DEG C of firings3N4Obtained g-C after being reduced for presoma3N4With the reduction of embodiment 1
g-C3N4The Yield comparison of hydrogen peroxide in illumination 1h systems.Traditional high-temperature firing g-C3N4The technique of presoma, such as
550 DEG C are fired obtained g-C3N4Presoma, then equally using the restoring method of the step of the embodiment of the present invention 1 (2) to the forerunner
Body is reduced, and is obtained 550 DEG C and is fired obtained g-C3N4The g-C of presoma after carrying out reduction3N4Based photocatalyst, and by its with
Embodiments of the invention 1 fire obtained g-C at 450 DEG C3N4The g-C for the modification that presoma obtains through step (2) reduction3N4Base
Photochemical catalyst is compared.
With the g-C of the 550 DEG C of firings generally prepared at present3N4For presoma after reduction obtained catalyst, i.e., according to
G-C made from the method for comparative example 13N4Based photocatalyst, hydrogen peroxide gas production is tested according to the identical method of embodiment 1, instead
The system is answered to be：100mL deionized waters are added in 250mL beakers, then weigh 0.1g catalyst, are stirred 2 hours under dark condition
Afterwards, irradiated with 300W xenon lamps, sampled every half an hour and survey concentration of hydrogen peroxide.
It can be seen from figure 7 that the g-C fired under the conditions of 550 DEG C3N4It is that presoma passes through reduction again, although after reduction
Valence band and conduction band positions also have change, but due to firing at this temperature so that valence band and conduction band positions still can not reach suitable
Position, valence band still can not aoxidize water after reduction, so yields of hydrogen peroxide is still very low in pure aquatic system, photocatalysis 1h
Concentration only reaches 23 μm of ol/L, and low temperature g-C made from embodiment 13N4After reduction, photocatalysis 1h concentration reaches 175 μ
Mol/L, effect promoting is close to 9 times.Thus step of the present invention (1) is also embodied in 400~500 DEG C of firing g-C of low temperature3N4Before
The necessity of body is driven, illustrates the g-C of the modification of the present invention3N4The preparation of visible-light photocatalyst is not only needed g-C3N4Forerunner
Body is reduced, and to g-C3N4The preparation technology of presoma also requires, the g-C of modification of the invention3N4Visible ray light is urged
Agent function admirable, production amount of hydrogen peroxide is big, is two step coordinateds of presoma burning process and reducing process, common to rise
The result of effect.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (10)
- A kind of 1. g-C of modification3N4Base visible-light photocatalyst, it is characterised in that the direct band gap width of the photochemical catalyst is 2.4~2.7eV, indirect band gap width are 1.7~2.65eV.
- 2. photochemical catalyst as claimed in claim 1, it is characterised in that the photochemical catalyst can directly absorbing wavelength be 550nm visible ray, and the visible ray of whole visible region can be absorbed indirectly.
- 3. photochemical catalyst as claimed in claim 1 or 2, it is characterised in that C ≡ N are included in the photocatalyst elements structure, Its infrared spectrum is in 2180cm-1Position there is C ≡ N peak.
- 4. the g-C of the modification as described in claims 1 to 3 any one3N4The preparation method of base visible-light photocatalyst, it is special Sign is, comprises the following steps：(1) substance A is fired into 3~5 hours under the conditions of 400 DEG C~500 DEG C, presoma g-C is obtained after washing3N4；The thing Matter A can produce the g-C of three s-triazine structures after 400 DEG C~500 DEG C polymerizations3N4；The substance A is preferably melamine or urine Element, more preferably melamine；(2) by step (1) obtained by presoma g-C3N4Mix with reducing agent, reduce under an inert atmosphere, can be obtained after washing The g-C of modification as described in claims 1 to 3 any one3N4Base visible-light photocatalyst.
- 5. preparation method as claimed in claim 4, it is characterised in that heating rate controls when step (1) fires melamine In 3~15 DEG C/min.
- 6. preparation method as claimed in claim 4, it is characterised in that step (2) described reducing agent is NaBH4Or KBH4, preferably For NaBH4。
- 7. preparation method as claimed in claim 6, it is characterised in that step (2) the presoma g-C3N4With the NaBH4 The mass ratio of mixing is 1:(2~6).
- 8. preparation method as claimed in claim 4, it is characterised in that step (2) described reduction temperature is 300 DEG C~400 DEG C, Preferably 370 DEG C.
- 9. preparation method as claimed in claim 4, it is characterised in that step (2) recovery time is 20min~40min, Preferably 30min.
- 10. the application of a kind of photochemical catalyst as described in claims 1 to 3 any one, it is characterised in that applied to photocatalysis Produce hydrogen peroxide.
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