CN104549403A - Composite photocatalyst-DyVO4/g-C3N4 and preparation method thereof - Google Patents
Composite photocatalyst-DyVO4/g-C3N4 and preparation method thereof Download PDFInfo
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- CN104549403A CN104549403A CN201410704811.XA CN201410704811A CN104549403A CN 104549403 A CN104549403 A CN 104549403A CN 201410704811 A CN201410704811 A CN 201410704811A CN 104549403 A CN104549403 A CN 104549403A
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Abstract
The invention discloses a method for preparing a composite photocatalyst-DyVO4/g-C3N4 and the composite photocatalyst prepared by adopting the method. The raw materials used in the method are readily available, the preparation conditions are easy to realize, and the prepared composite photocatalyst is high in catalytic efficiency under visible light catalysis conditions.
Description
Technical field
The invention belongs to photocatalysis field, relate to a kind of preparation method of photochemical catalyst, particularly one prepares composite photo-catalyst DyVO
4/ g-C
3n
4method.
Background technology
In recent years, along with industrial fast development, problem of environmental pollution is subject to the common concern of people always.Along with administering improving constantly of industrial pollution technology, photocatalysis technology, namely utilizes solar energy to carry out the research of Photocatalyst in environmental improvement to pollutant more and more deep.
Another thinking of research photochemical catalyst finds novel photocatalyst.But, experimental results demonstrate, not high as the photocatalysis efficiency of photochemical catalyst using one matter merely, and the catalytic effect of composite photocatalyst strengthens to some extent.
Therefore, seeking two kinds can compound, and the compound that after compound, photocatalysis effect strengthens and preparation method thereof, and seeks weight ratio suitable between them and make the photocatalysis effect of compound reach optimum, becomes the new problem of photocatalysis field.
Summary of the invention
In order to solve the problem, present inventor has performed and study with keen determination, found that: after graphite phase carbon nitride and positive vanadic acid dysprosium make compound, it improves compared to simple graphite phase carbon nitride the Photocatalytic activity of dye wastewater.
The object of the present invention is to provide following aspect:
First aspect, the invention provides one and prepares composite photo-catalyst DyVO
4/ g-C
3n
4method, it is characterized in that, the method comprises the following steps:
(1) by itrogenous organic substance roasting at 300 ~ 800 DEG C, cooling, obtained product I;
(2) water-soluble after metavanadate being mixed with dysprosium salt, regulate pH value of solution to neutral, filter after leaving standstill, will roasting at 400 ~ 900 DEG C after product drying be filtered to obtain, cooling, obtained product II;
(3) product I is mixed with product II, then roasting at the mixture obtained grinding is placed on 400 ~ 900 DEG C, cooling, obtained composite photo-catalyst.
Second aspect, the composite photo-catalyst DyVO that the present invention also provides a kind of method according to above-mentioned first aspect obtained
4/ g-C
3n
4, it is characterized in that,
In described composite photo-catalyst, based on the gross weight of composite photo-catalyst, the weight fraction of vanadic acid dysprosium is 0.1% ~ 30%, is preferably 0.3% ~ 25%, as 0.5%, 1%, 2.5%, 5%, 10%, 15% and 20%; And/or
According to solid phase fluorescent spectrum, it is there is strong absworption peak near 460nm at wavelength; And/or
According to UV-Vis diffuse reflection spectroscopy, it is existing characteristics absorption band near 600nm and near 750nm at wavelength.
Accompanying drawing explanation
Fig. 1 a illustrates the transmission electron microscope picture of the sample that comparative example 1 is obtained;
Fig. 1 b illustrates the transmission electron microscope picture of the sample that embodiment 4 is obtained;
Fig. 2 illustrates the infrared spectrogram of sample, wherein,
Embodiment 1 obtains sample and represents by 0.5%;
Embodiment 2 obtains sample and represents by 1%;
Embodiment 4 obtains sample and represents by 5%;
Embodiment 6 obtains sample and represents by 15%;
Embodiment 7 obtains sample and represents by 20%;
Comparative example 1 obtains sample by g-C
3n
4represent;
Comparative example 2 obtains sample by DyVO
4represent;
Fig. 3 illustrates the solid phase fluorescent spectrogram of sample, wherein,
Embodiment 3 obtains sample and is represented by curve b;
Embodiment 4 obtains sample and is represented by curve a;
Embodiment 6 obtains sample and is represented by curve c;
Embodiment 7 obtains sample and is represented by curve e;
Comparative example 1 obtains sample and is represented by curve d;
Comparative example 2 obtains sample and is represented by curve f;
Fig. 4 illustrates the UV-vis DRS spectrum of sample, wherein,
Embodiment 4 obtains sample and is represented by curve b;
Comparative example 1 obtains sample and is represented by curve a;
Fig. 5 illustrates the visible light catalysis activity (methyl orange) of different catalysts, wherein,
Comparative example 1 obtains sample and is represented by curve a;
Embodiment 2 obtains sample and is represented by curve b;
Embodiment 3 obtains sample and is represented by curve c;
Embodiment 4 obtains sample and is represented by curve d;
Embodiment 5 obtains sample and is represented by curve e;
Embodiment 6 obtains sample and is represented by curve f;
Embodiment 7 obtains sample and is represented by curve g;
Fig. 6 illustrates the impact of scavenger on composite photo-catalyst activity, wherein,
None represents and does not add scavenger,
AO represents ammonium oxalate,
BQ represents 1,4-benzoquinone,
CAT represents catalase,
IPA represents isopropyl alcohol.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will illustrate along with these and become more clear, clear and definite.
Class graphitic nitralloy carbon (is called for short g-C
3n
4) molecule be layer structure as graphite, every one deck molecular layer forms network structure by nitrogen-atoms and carbon atom, and wherein the ratio of nitrogen and carbon is close to 1:1.
According to a first aspect of the invention, one is provided to prepare composite photo-catalyst DyVO
4/ g-C
3n
4method, the method comprises the following steps:
Step 1, by itrogenous organic substance roasting at 300 ~ 800 DEG C, cooling, obtained product I.
Simultaneously containing nitrogen element and carbon in itrogenous organic substance, that is, itrogenous organic substance is being prepared in graphite phase carbon nitride not only as nitrogen source but also as carbon source material.
The present inventor finds, uses the itrogenous organic substance of the small-molecular-weight that carbon-nitrogen ratio is 1:3 ~ 3:1 as raw material, preferably uses the small-molecular-weight itrogenous organic substance that carbon-nitrogen ratio is 1:2 as raw material, in 300 ~ 800 DEG C of environment, can obtain cancellated g-C after roasting
3n
4, as cyanamide, dicyanodiamine, melamine, urea, guanidine hydrochloride etc., be preferably urea.
The present inventor finds through large quantity research, and urea starts hydrolysis under about 60 DEG C of conditions, and after heating up, hydrolysis accelerates, and after desolventizing, this hydrolysate or the urea being mixed with this hydrolysate easily generate g-C under roasting condition
3n
4, in addition, urea low price, easily obtains, and it is at generation g-C
3n
4other accessory substance rear is few, i.e. product g-C
3n
4middle impurity is few, and be beneficial to the purity improving follow-up compound, therefore, the present invention preferably uses urea, more preferably before roasting, is dissolved in the water by urea, and heats at 20 ~ 80 DEG C.
The present inventor also finds, when sintering temperature is 300 ~ 800 DEG C, obtained product morphology is homogeneous, layer structure is obvious, and the photocatalysis efficiency of the composite photo-catalyst obtained with this condition is high, therefore, it is 350 ~ 700 DEG C that the present invention preferably burns temperature, is more preferably 400 ~ 600 DEG C, as 450 DEG C.
The present inventor finds further, and roasting time is can fully react for 1 ~ 5 hour, and therefore, the present invention preferably selected roasting time to be 1.5 ~ 4 hours, is more preferably 2 ~ 3.5 hours, as 3 hours.
In a preferred embodiment of the invention, select in confined conditions to the roasting that raw material carries out, avoid raw material too to contact with oxygen, thus the significant loss reducing raw material complete oxidation and bring.
Step 2, water-soluble after metavanadate is mixed with dysprosium salt, regulate pH value of solution to neutral, filter after leaving standstill, will roasting at 400 ~ 900 DEG C after product drying be filtered to obtain, cooling, obtained product II.
The present invention selects the dysprosium salt of the metavanadate of solubility and solubility to react in aqueous phase system, obtained product is at neutral water, be preferably pH=6 ~ 8, be more preferably pH=6.5 ~ 7.5, as little in the solubility in the water of pH=7, separate out with the form precipitated, other accessory substance then has good dissolubility in water, thus this precipitation can be separated from system by the method for filtering, then this product roasting can be obtained the product II containing vanadic acid dysprosium.
The solubility metavanadate that the present invention selects is selected from sodium metavanadate, potassium metavanadate and ammonium metavanadate, is preferably ammonium metavanadate.
The present invention selects solubility dysprosium salt to be selected from dysprosium nitrate and dysprosium chloride, is preferably dysprosium nitrate.
The mole of metavanadate is with the molar amount of wherein v element, and the mole of dysprosium salt is with the molar amount of wherein dysprosium element, and the present invention selects the mole of metavanadate to be 1:3 ~ 3:1 with the ratio of the mole of dysprosium salt, is preferably 1:2 ~ 2:1, as 1:1.
The present inventor finds, reaction system, in time neutral, is easy to precipitation, use weakly alkaline solution regulation system pH that the pH change of system can be avoided too fast, thus avoid inclusion impurity in precipitation, therefore, choice for use ammoniacal liquor of the present invention, sodium acetate, sodium phenate etc., preferably use ammoniacal liquor.
The present inventor finds, after metavanadate and dysprosium salt reacts and generates and precipitate in aqueous phase system, standing a period of time, precipitate more abundant, and be easy to filtration, therefore, the present invention selected time of repose to be 0.5 ~ 5 hour, preferably 1 ~ 3 hour, as 2 hours.
By the sedimentation and filtration obtained in aqueous phase system, before roasting, carry out drying, baking temperature is 50 ~ 150 DEG C, and be preferably 80 ~ 120 DEG C, as 100 DEG C, drying time is 5 ~ 20 hours, is preferably 8 ~ 18 hours, as 12 hours.
The present inventor find, dried sediment under temperature is 400 ~ 900 DEG C of conditions, DyO in the product obtained
4content high, the pattern of product is homogeneous, and therefore, the preferred sintering temperature of the present invention is 450 ~ 800 DEG C, is more preferably 500 ~ 700 DEG C.
Be 0.5 ~ 5 constantly little upon firing, can obtain product II, therefore, the present invention preferably selected roasting time to be 1 ~ 4 hour, is more preferably 1.5 ~ 3.5 hours, as 2 hours.
Step 3, mixes product I with product II, then roasting at the mixture obtained grinding is placed on 400 ~ 900 DEG C, cooling, obtained composite photo-catalyst.
Take product I and product II respectively, mix, make in the composite photo-catalyst obtained, based on the gross weight of composite photo-catalyst, with the weighing scale of vanadic acid dysprosium, wherein the weight fraction of vanadic acid dysprosium is 0.1% ~ 30%, is preferably 0.3% ~ 25%, as 0.5%, 1%, 2.5%, 5%, 10%, 15% and 20%.
Ground by said mixture, product I and product II is mixed to get more abundant, is convenient to the preparation of follow-up compound, the present invention selects milling time to be 10min ~ 2 hour, is preferably 20min ~ 1 hour, as 30min.
Under sintering temperature is 400 ~ 900 DEG C of conditions, obtained compound pattern is homogeneous, and photocatalysis efficiency strengthens obviously, and therefore, the preferred sintering temperature of the present invention is 450 ~ 800 DEG C, as 500 DEG C.
The present invention selects roasting time to be 1 ~ 5 hour, is preferably 1.5 ~ 4 hours, as 2 hours.
The composite photo-catalyst obtained by above step,
According to red-light spectrum, this composite photo-catalyst is 817cm in wave number
-1in neighbouring existence, strong peak, is 1252cm in wave number
-1near there is weak peak, be 1388cm in wave number
-1strong peak in neighbouring existence, at 1637cm
-1near there is strong peak, at 3420cm
-1near there is wide and strong peak;
According to solid phase fluorescent spectrum, it is there is strong absworption peak near 460nm at wavelength;
According to UV-Vis diffuse reflection spectroscopy, it is existing characteristics absorption band near 600nm and near 750nm at wavelength.
According to a second aspect of the invention, provide by the obtained composite photo-catalyst of method described in above-mentioned first aspect.
In described composite photo-catalyst, based on the gross weight of composite photo-catalyst, the weight fraction of vanadic acid dysprosium is 0.1% ~ 30%, is preferably 0.3% ~ 25%, as 0.5%, 1%, 2.5%, 5%, 10%, 15% and 20%; And/or
According to red-light spectrum, this composite photo-catalyst is 817cm in wave number
-1in neighbouring existence, strong peak, is 1252cm in wave number
-1near there is weak peak, be 1388cm in wave number
-1strong peak in neighbouring existence, at 1637cm
-1near there is strong peak, at 3420cm
-1near there is wide and strong peak; And/or
According to solid phase fluorescent spectrum, it is there is strong absworption peak near 460nm at wavelength; And/or
According to UV-Vis diffuse reflection spectroscopy, it is existing characteristics absorption band near 600nm and near 750nm at wavelength.
According to composite photo-catalyst DyVO provided by the invention
4/ g-C
3n
4and preparation method thereof, there is following beneficial effect:
(1) under visible light catalytic, it is to organic dyestuff, and particularly azo dyes has degradation;
(2) method preparing this composite photo-catalyst is easy, and bulk drug is cheap and easy to get;
(3) this composite photo-catalyst and preparation method thereof environmental protection, non-environmental-pollution.
Embodiment
the preparation (0.5%) of embodiment 1 composite photo-catalyst
(1) take 15.0g melamine and put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 5h under 500 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 2mol ammonium metavanadate and the mixing of 1mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 8.0 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 1h, continues 12h, then move in alumina crucible, be placed in Muffle furnace in 400 DEG C of roasting 3h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 80 DEG C
4, i.e. product II.
(3) accurately take 0.0050g product II and 0.9950g product I, mix in agate mortar and after grinding 30min, proceed to alumina crucible, roasting 2h at 500 DEG C, room temperature cools, and can obtain 0.5%DyVO
4/ g-C
3n
4(wherein, 0.5% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (1%) of embodiment 2 composite photo-catalyst
(1) small beaker that 15.0g urea is placed in dried and clean is taken, be dissolved in 20mL distilled water, isothermal reaction in 60 DEG C of water-baths, after aqueous solvent evaporate to dryness, the sample obtained is put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 5h under 400 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1mol ammonium metavanadate and the mixing of 2mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 7.5 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 3h, continues 10h, then move in alumina crucible, be placed in Muffle furnace in 700 DEG C of roasting 3h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 120 DEG C
4, i.e. product II.
(3) accurately take 0.0100g product II and 0.9900g product I, mix in agate mortar and after grinding 1 hour, proceed to alumina crucible, roasting 3h at 600 DEG C, room temperature cools, and can obtain 1.0%DyVO
4/ g-C
3n
4(wherein, 1.0% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (2.5%) of embodiment 3 composite photo-catalyst
(1) take 15.0g dicyanodiamine and put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 4h under 300 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1mol ammonium metavanadate and the mixing of 1.5mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 6.5 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 2h, continues 18h, then move in alumina crucible, be placed in Muffle furnace in 900 DEG C of roasting 2h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 110 DEG C
4, i.e. product II.
(3) accurately take 0.0250g product II and 0.9750g product I, mix in agate mortar and after grinding 1 hour, proceed to alumina crucible, roasting 3h at 600 DEG C, room temperature cools, and can obtain 2.5%DyVO
4/ g-C
3n
4(wherein, 2.5% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (5%) of embodiment 4 composite photo-catalyst
(1) small beaker that 15.0g urea is placed in dried and clean is taken, be dissolved in 20mL distilled water, isothermal reaction in 80 DEG C of water-baths, after aqueous solvent evaporate to dryness, the sample obtained is put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 3h under 450 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1mol ammonium metavanadate and the mixing of 1mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 7.0 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 2h, continues 12h, then move in alumina crucible, be placed in Muffle furnace in 500 DEG C of roasting 2h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 100 DEG C
4, i.e. product II.
(3) accurately take 0.0500g product II and 0.9500g product I, mix in agate mortar and after grinding 30min, proceed to alumina crucible, roasting 2h at 500 DEG C, room temperature cools, and can obtain 5%DyVO
4/ g-C
3n
4(wherein, 5% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (10%) of embodiment 5 composite photo-catalyst
(1) small beaker that 15.0g urea is placed in dried and clean is taken, be dissolved in 20mL distilled water, isothermal reaction in 70 DEG C of water-baths, after aqueous solvent evaporate to dryness, the sample obtained is put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 3.5h under 300 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1.5mol ammonium metavanadate and the mixing of 1mol dysprosium nitrate, be dissolved in respectively in distilled water, use sodium acetate regulation system pH to 6.0 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 5h, continues 5h, then move in alumina crucible, be placed in Muffle furnace in 800 DEG C of roasting 2h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 150 DEG C
4, i.e. product II.
(3) accurately take 0.1000g product II and 0.9000g product I, mix in agate mortar and after grinding 30min, proceed to alumina crucible, roasting 2h at 500 DEG C, room temperature cools, and can obtain 10%DyVO
4/ g-C
3n
4(wherein, 10% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (15%) of embodiment 6 composite photo-catalyst
(1) small beaker that 15.0g urea is placed in dried and clean is taken, be dissolved in 20mL distilled water, isothermal reaction in 75 DEG C of water-baths, after aqueous solvent evaporate to dryness, the sample obtained is put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 3h under 600 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1mol ammonium metavanadate and the mixing of 1mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 7.0 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 3h, continues 14h, then move in alumina crucible, be placed in Muffle furnace in 800 DEG C of roasting 2h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 130 DEG C
4, i.e. product II.
(3) accurately take 0.1500g product II and 0.8500g product I, mix in agate mortar and after grinding 20min, proceed to alumina crucible, roasting 2h at 700 DEG C, room temperature cools, and can obtain 15%DyVO
4/ g-C
3n
4(wherein, 15% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
the preparation (20%) of embodiment 7 composite photo-catalyst
(1) small beaker that 15.0g urea is placed in dried and clean is taken, be dissolved in 20mL distilled water, isothermal reaction in 65 DEG C of water-baths, after aqueous solvent evaporate to dryness, the sample obtained is put into alumina crucible (adding a cover), be placed in Muffle furnace, roasting 3h under 450 DEG C of conditions, naturally cools to room temperature, obtains g-C
3n
4sample, i.e. product I.
(2) by 1mol ammonium metavanadate and the mixing of 1.5mol dysprosium nitrate, be dissolved in respectively in distilled water, use ammoniacal liquor regulation system pH to 7.0 by after two kinds of solution mixing, have yellow absurd creature to generate; Room temperature is filtered after leaving standstill 2h, continues 12h, then move in alumina crucible, be placed in Muffle furnace in 500 DEG C of roasting 2h, naturally cool to room temperature, obtain light tan solid DyVO at putting into vacuum drying oven 100 DEG C
4, i.e. product II.
(3) accurately take 0.2000g product II and 0.8000g product I, mix in agate mortar and after grinding 3 hours, proceed to alumina crucible, roasting 2h at 500 DEG C, room temperature cools, and can obtain 20%DyVO
4/ g-C
3n
4(wherein, 20% represents DyVO to catalyst prod
4at DyVO
4/ g-C
3n
4in percetage by weight).
Comparative example
comparative example 1
This comparative example is by the obtained g-C of the method for step (1) in embodiment 4
3n
4sample.
comparative example 2
This comparative example is by the obtained DyVO of the method for step (2) in embodiment 4
4sample.
Experimental example
the transmission electron microscope picture of experimental example 1 sample
This experimental example specimen in use is the sample that comparative example 1 and embodiment 4 obtain.
Measure catalyst pattern with CM200-FEG type transmission electron microscope (TEM, accelerating potential 200kV, Philips company), as illustrated in figs. ia and ib, wherein, Fig. 1 a illustrates the pattern of the sample that comparative example 1 is obtained to result; Fig. 1 b illustrates that embodiment 4 obtains the pattern of sample, from Fig. 1 a and Fig. 1 b,
Sample g-C obtained in comparative example 1
3n
4as the carrier of composite photo-catalyst, it has comparatively regular geometric shape and less particle diameter, the domain size distribution also relative narrower of particle;
And the sample that embodiment 4 is obtained, its particle size differs, and particle size distribution range is wider, DyVO
4at g-C
3n
4the distribution of carrier surface also and uneven, obtains sample from comparative example and demonstrates significantly different on pattern.
the infrared spectrogram of experimental example 2 sample
This experimental example specimen in use is that embodiment 1 (representing with 0.5%), embodiment 2 (representing with 1%), embodiment 4 (representing with 5%), embodiment 6 (representing with 15%), embodiment 7 (representing with 20%) and comparative example 1 are (with g-C
3n
4represent), comparative example 2 is (with DyVO
4represent) obtained sample.
With WQF-501 FTIS, infrared spectrum characterization experiment (KBr compressing tablet) is carried out to sample, result as shown in Figure 2, as shown in Figure 2:
Be 1200cm in wave number
-1-1380cm
-1between peak be the stretching vibration peak of C-N, at 1380cm
-1-1690cm
-1the peak at place is the stretching vibration peak of C=N, at 817cm
-1neighbouring peak is the flexural vibrations peak of synthesize, at 3000cm
-1-3500cm
-1the peak at place is NH-and NH
2-stretching vibration peak, in embodiment 1,2,4,6 and 7, obtained sample obtained sample peak intensity in this wave-number range in the peak intensity of above-mentioned wavenumber range is relative to comparative example 1 and 2 obviously strengthens.
1637cm in figure
-1and 3420cm
-1neighbouring absworption peak corresponds to shearing and the stretching vibration absworption peak of hydroxyl, and, at 1637cm
-1near there is small absworption peak, show composite photo-catalyst surface exist trace adsorbed water.
Wherein, 5%DyVO
4/ g-C
3n
4composite photo-catalyst (embodiment 4 obtains sample) is at 817cm
-1near occur that absworption peak is comparatively obvious.
In addition, obtained in each embodiment 1,2,4,6 and 7 composite photo-catalyst is at 1252cm
-1near all there is absorption, and it is the strongest to obtain the absworption peak of sample with embodiment 4 in the absworption peak of these different catalysts, and be not bound by any theory, the present inventor thinks that this is the reason that composite photo-catalyst has relatively high photocatalytic activity.
the solid phase fluorescent spectrogram of experimental example 3 sample
This experimental example specimen in use be embodiment 3 (curve b), embodiment 4 (curve a), obtained in embodiment 6 (curve c) and embodiment 7 (curve e) and comparative example 1 (curve d) and comparative example 2 (curve f) sample.
Experimental technique:
Get appropriate (filling the elliptical slot of film pressure plate, unnecessary recovery) 2.5%DyVO
4/ g-C
3n
4, 5%DyVO
4/ g-C
3n
4, 15%DyVO
4/ g-C
3n
4, 20%DyVO
4/ g-C
3n
4, DyVO
4, g-C
3n
4type catalyst sample (powder), adopts MDX1000 XRF to test the photoluminescence performance of various catalyst sample, test result as shown in Figure 3, as shown in Figure 3:
DyVO
4/ g-C
3n
4type composite photo-catalyst has absorption to visible ray, its order of absorbability to visible ray is: a>b>c>eGreatT. GreaT.GTd>f, the activity of composite photo-catalyst is all greater than simple g-C
3n
4catalytic activity, and simple DyVO
4almost visible ray can not be absorbed, in composite photo-catalyst, along with DyVO
4the increase of load capacity, the absorption of composite photo-catalyst to visible ray first strengthens, and works as DyVO
4at DyVO
4/ g-C
3n
4weight fraction when reaching 5%, it is the strongest to visible absorption ability, then along with DyVO
4at DyVO
4/ g-C
3n
4in weight fraction increase and weaken, be not bound by any theory, the present inventor thinks because excessive DyVO
4hamper g-C
3n
4to the absorption of visible ray.
With simple DyVO
4or g-C
3n
4compare, 5%DyVO
4/ g-C
3n
4photochemical catalyst has stronger visible absorption performance in 400-700nm region and ABSORPTION EDGE moves to long wave direction.
the UV-Vis diffuse reflection spectroscopy of experimental example 4 sample
This experimental example specimen in use is sample obtained in embodiment 4 and comparative example 1.
This experimental example uses TU-1901 dual-beam ultraviolet-visible spectrophotometer to measure catalyst UV-Visible diffuse spectrum.
Method of operating:
First open instrument, carry out self-inspection; Then carry out baseline correction (two light path is all using water as reference), from " measurement " tab, carry out optimum configurations, after setting parameter, carry out baseline correction; After baseline correction is good, in two light paths, put into g-C to be measured respectively
3n
4(comparative example 1 obtains sample, curve a), 5%DyVO
4/ g-C
3n
4(embodiment 4 obtains sample, curve b), select " time sweep " option, then carry out optimum configurations, start test, test result as shown in Figure 4, as shown in Figure 4:
5%DyVO
4/ g-C
3n
4(embodiment 4 obtains sample to composite photo-catalyst, represented by curve b) obtain sample (curve a) compared to comparative example 1, it has larger absorbing properties within the scope of 200-800nm, and its absorption edge moves (red shift) to long wave direction gradually, 600nm place appearance absorption band is about at wavelength, the bands of a spectrum be about near 730nm at wavelength are covered by the bands of a spectrum that wavelength is about near 750nm, be not bound by any theory, the present inventor thinks that above-mentioned experimental result is 5%DyVO
4/ g-C
3n
4composite photo-catalyst has a reason of stronger photocatalytic activity.
the visible light catalysis activity (methyl orange) of experimental example 5 different catalysts
This experimental example specimen in use is embodiment 2 (label b), 3 (label c), 4 (label d), 5 (label e), 6 (label f), 7 (label g) and the comparative example 1 (sample that label is a) obtained.
Experimental technique:
Accurately take 0.050g DyVO
4/ g-C
3n
4(X=20%, 15%, 10%, 5%, 2.5%, 1%, X is DyVO
4at DyVO
4/ g-C
3n
4in weight percent) catalyst fines is in quartz ampoule, numbering respectively, is 5.00mgL respectively to adding 40mL concentration in quartz ampoule
-1methyl orange solution, and add a little magneton, quartz ampoule is put into photochemical reaction instrument, under continuous stirring, dark treatment 30min, samples centrifugal, surveys its absorbance A respectively
0, open light source (having added optical filter), visible photo-irradiation treatment 0.5h, samples centrifugal, surveys its absorbance A
t, calculate degradation rate according to following formula I:
W (%)=(A
0-A
t)/A
0× 100% formula I
The visible light activity figure of different catalysts sample is drawn out according to gained degradation rate, as shown in Figure 5, as shown in Figure 5:
DyVO after compound
4/ g-C
3n
4the g-C that the visible light catalysis activity of photochemical catalyst is purer
3n
4all increase, illustrate that this experiment is to g-C
3n
4modification effective.
In Fig. 5, DyVO
4/ g-C
3n
4the visible light catalysis activity of composite photo-catalyst is with DyVO
4percetage by weight increase and first increase, and at DyVO
4percetage by weight when being 5% the visible light catalysis activity of composite photo-catalyst peak, be at this moment 69.5% to Photocatalytic Degradation of Methyl Orange rate, then visible light catalysis activity is again with DyVO
4mass percent increase and reduce.
the visible light catalysis activity (rhodamine B) of experimental example 6 different catalysts
This experimental example specimen in use is the sample that embodiment 4 obtains.
Experimental technique:
Light-catalyzed reaction carries out in an XPA photochemical reaction instrument, adds the obtained composite photo-catalyst sample of 0.05g embodiment 4 and 40mL rhodamine B solution (5.00mgL in the interlayer reactor passing into cooling water
-1), then put into a little magneton, pass into cooling water and maintain reaction temperature 25 DEG C, under continuous stirring, after dark reaction 30min, sample centrifugal, measure its absorbance A
0; Open 300W high-pressure sodium lamp (interpolation optical filter) and use visible photo-irradiation treatment 0.5h, 1h and 1.5h respectively, carry out centrifugation, measure its absorbance A
t; The degradation rate of catalyst sample is calculated according to following formula I,
W (%)=(A
0-A
t)/A
0× 100% formula I
As radiation of visible light 0.5h, the photocatalytic activity of rhodamine B reaches 74.8%, and as visible photo-irradiation treatment 1.5h, rhodamine B is completely degraded, and namely degradation rate reaches 100%.
experimental example 7 scavenger is on the impact of catalyst degradation methyl orange activity
This experimental example specimen in use is the sample that embodiment 4 obtains.
O
2 -be introduced into reaction system by scavenger 1,4-benzoquinone (BQ), OH is introduced in reaction system, h by scavenger isopropyl alcohol (IPA)
+reaction system is introduced in, H by scavenger ammonium oxalate (AO)
2o
2be eliminated agent catalase (CAT) and also introduced reaction system respectively.
Experimental technique:
Accurately take 0.050g 5%DyVO
4/ g-C
3n
4composite photo catalyst powder is in quartz ampoule, and numbering None, AO, BQ, CAT and IPA, adding 40mL concentration respectively is successively 5.00mgL
-1methyl orange solution, 5.000 μ L isopropyl alcohols are added in IPA pipe, in AO pipe, add 0.004g ammonium oxalate, in BQ pipe, add 0.004g 1,4-benzoquinone, in CAT pipe, add 3.800 μ L catalases, each Guan Zhongjun adds a little magneton, quartz ampoule is put into photochemical reaction instrument, under continuous stirring, dark treatment 30min, sample centrifugal, survey its absorbance A respectively
0; Open light source, ultraviolet lighting process 0.5h, samples centrifugal, surveys its absorbance A
t, calculate degradation rate according to following formula I:
W (%)=(A
0-A
t)/A
0× 100% formula I
Result of calculation is plotted as block diagram, as shown in Figure 6, as shown in Figure 6:
Adding the impact of catalyst visible light activity of ammonium oxalate (AO), catalase (CAT) and 1,4-benzoquinone (BQ) is very little, almost can ignore, that is, when other conditions are identical, H in the process of photo-catalytic degradation of methyl-orange under visible light illumination
2o
2, h+, O
2 -it not main active specy.
And add isopropyl alcohol (IPA) in reaction system after, the activity of composite photo-catalyst has and comparatively significantly reduces, and that is, OH plays a major role in photocatalytic process.
More than in conjunction with detailed description of the invention and exemplary example to invention has been detailed description, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that when not departing from spirit and scope of the invention, can carry out multiple equivalencing, modification or improvement to technical solution of the present invention and embodiment thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. prepare composite photo-catalyst DyVO for one kind
4/ g-C
3n
4method, it is characterized in that, the method comprises the following steps:
(1) by itrogenous organic substance roasting at 300 ~ 800 DEG C, cooling, obtained product I;
(2) water-soluble after metavanadate being mixed with dysprosium salt, regulate pH value of solution to neutral, filter after leaving standstill, will roasting at 400 ~ 900 DEG C after product drying be filtered to obtain, cooling, obtained product II;
(3) product I is mixed with product II, then roasting at the mixture obtained grinding is placed on 400 ~ 900 DEG C, cooling, obtained composite photo-catalyst.
2. method according to claim 1, is characterized in that, in step (1), itrogenous organic substance is selected from cyanamide, dicyanodiamine, melamine, urea and guanidine hydrochloride, is preferably urea.
3. method according to claim 1 and 2, is characterized in that, in step (1), heats itrogenous organic substance roasting being prepended in water, then except anhydrating.
4., according to the method one of claims 1 to 3 Suo Shu, it is characterized in that, in step (1), at 350 ~ 700 DEG C, preferably roasting at 400 ~ 600 DEG C.
5. according to the method one of Claims 1-4 Suo Shu, it is characterized in that, in step (2), metavanadate is solubility metavanadate, is preferably selected from sodium metavanadate, potassium metavanadate and ammonium metavanadate, is more preferably ammonium metavanadate.
6. according to the method one of claim 1 to 5 Suo Shu, it is characterized in that, in step (2), dysprosium salt is solubility dysprosium salt, is preferably selected from dysprosium nitrate and dysprosium chloride, is more preferably dysprosium nitrate.
7. according to the method one of claim 1 to 6 Suo Shu, it is characterized in that, in step (2), use ammoniacal liquor, sodium acetate and/or sodium phenate regulation system pH, preferably use ammoniacal liquor.
8. according to the method one of claim 1 to 7 Suo Shu, it is characterized in that, in step (3), take product I and product II respectively, mix, obtain mixture, make in the composite photo-catalyst obtained, based on the gross weight of composite photo-catalyst, the weight fraction of vanadic acid dysprosium is 0.1% ~ 30%, be preferably 0.3% ~ 25%, as 0.5%, 1%, 2.5%, 5%, 10%, 15% and 20%.
9. according to the method one of claim 1 to 8 Suo Shu, it is characterized in that, composite photo-catalyst obtained in step (3),
According to solid phase fluorescent spectrum, it is there is strong absworption peak near 460nm at wavelength; And/or
According to UV-Vis diffuse reflection spectroscopy, it is existing characteristics absorption band near 600nm and near 750nm at wavelength.
10. the composite photo-catalyst that the method according to any one of claim 1 ~ 9 is obtained, is characterized in that,
In described composite photo-catalyst, based on the gross weight of composite photo-catalyst, the weight fraction of vanadic acid dysprosium is 0.1% ~ 30%, is preferably 0.3% ~ 25%, as 0.5%, 1%, 2.5%, 5%, 10%, 15% and 20%; And/or
According to solid phase fluorescent spectrum, it is there is strong absworption peak near 460nm at wavelength; And/or
According to UV-Vis diffuse reflection spectroscopy, it is existing characteristics absorption band near 600nm and near 750nm at wavelength.
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| CN105195194A (en) * | 2015-08-12 | 2015-12-30 | 阜阳师范学院 | Photocatalyst composition CNB-BiVO4 and preparation method and application thereof |
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| CN105195190A (en) * | 2015-07-06 | 2015-12-30 | 阜阳师范学院 | Heterojunction photocatalyst SnS2/g-C3N4 as well as preparation method and application thereof |
| CN105478153A (en) * | 2015-11-30 | 2016-04-13 | 南京理工大学 | CeVO4 / Ag / g-C3N4 composite photocatalyst and preparation method thereof |
| CN111450861A (en) * | 2019-01-22 | 2020-07-28 | 阜阳师范学院 | Comprising g-C3N4Composite photocatalyst of B and metal oxide and application thereof in fuel oil denitrification |
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