A kind of BiVO4@CdIn2S4/g-C3N4Visible light responsive photocatalyst and preparation method thereof
Technical field
The present invention relates to photocatalysis technology fields, and in particular to a kind of BiVO4@CdIn2S4/g-C3N4Visible light-responded light
Catalyst and preparation method thereof.
Background technique
Energy shortage and environmental degradation are the two large problems of current facing mankind.With the rapid growth of energy demand, too
It is positive can utilize technology more and more attention has been paid to.Converting solar energy into chemical energy is a challenging job.Utilize light
Catalysis material carries out water decomposition hydrogen manufacturing, on the one hand can utilize light degradation organic pollutant, on the other hand directly solar energy is turned
Turn to Hydrogen Energy.Hydrogen can store, and the thermal efficiency is high, be ideal clean energy resource, be also important industrial chemicals.Photodegradation water hydrogen manufacturing energy
The generation of by-product carbon dioxide in existing hydrogen production process is enough avoided, it is more environmentally friendly.Therefore, catalysis material solve the energy and
There is dual application prospect in terms of environmental problem.
Existing catalysis material is generally TiO2Material, TiO2Only ultraviolet light response, and UV energy only accounts for the sun
4% or so of light energy, it is seen that the energy of light but accounts for the 43% of solar energy.In the research of last decade, it is seen that photoresponse
Photochemical catalyst is favored, and wherein metal sulfide is typically to represent.The forbidden bandwidth of metal sulfide is relatively narrow, chemical stabilization
Property it is good, visible light region have stronger light absorption, the utilization rate of luminous energy can be effectively improved.But simple metal sulfide
Photocatalytic activity it is lower.Inventor is the study found that other than visible light absorption capacity, the microscopic appearance of catalyst, photoproduction
The factors such as electron-hole pair conducting carrier, co-catalyst also function to very big influence to water decomposition reaction.
Summary of the invention
The purpose of the present invention is to provide a kind of BiVO4@CdIn2S4/g-C3N4The preparation side of visible light responsive photocatalyst
Method, with g-C3N4, multi-element metal sulfide CdIn2S4And BiVO4Hetero-junctions compound system is constructed, photogenerated charge separation effect is improved
Rate has good photocatalysis effect.
Another object of the present invention is to provide a kind of BiVO4@CdIn2S4/g-C3N4Visible light responsive photocatalyst, the light
Catalyst has good photocatalysis performance, and it is high to produce hydrogen effect.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of BiVO4@CdIn2S4/g-C3N4The preparation method of visible light responsive photocatalyst, including it is following
Step:
Few lamella g-C3N4Preparation: calcining is carried out to nitridation carbon matrix precursor and obtains few lamella g-C3N4;
Monolithic or few lamella CdIn2S4Preparation: divalent cadmium salt, trivalent indium salts and thioacetamide are distinguished according to molar ratio
It is dissolved in the first solvent, then mixes, heat 22-30h under the conditions of 140~200 DEG C, separated, washed, dried, ground
Reaction product is obtained after mill;The reaction product is placed in mixed liquor and is heated to reflux 1~3h, obtains monolithic or few lamella
CdIn2S4, wherein the mixed liquor is the aqueous solution containing sodium bicarbonate, isopropanol and polyvinylpyrrolidone;
CdIn2S4/g-C3N4Mixture preparation: by the g-C3N4With the CdIn2S4It mixes, is evaporated in the second solvent
Second solvent, is then dried to obtain CdIn2S4/g-C3N4Mixture;
BiVO4@CdIn2S4/g-C3N4Preparation: trivalent bismuth salt is dissolved in acetic acid solution and obtains the first solution, by inclined vanadium
Sour ammonium, which is dissolved in ammonia spirit, obtains the second solution, and is obtained after first solution and second solution are slowly mixed together
Three solution;The pH to 7~8 of the third solution is adjusted, the CdIn is added after stirring 30~60min2S4/g-C3N4Mixture,
After ultrasonic disperse, 2-4h is reacted under the conditions of 140~200 DEG C, is cooled and separated, washs, drying and grinding obtains BiVO4@
CdIn2S4/g-C3N4Visible light responsive photocatalyst.
Further, in preferred embodiments of the present invention, the step of calcining to nitridation carbon matrix precursor are as follows:
Be warming up to 500~550 DEG C with the first heating speed, calcine 1~3h, obtained calcined product through cooling, grind
To the first calcined material;Then,
First calcined material is warming up to 500~550 DEG C with the second heating rate, calcines 1~3h, obtained calcining produces
Object obtains few lamella g-C through cooling, grinding3N4。
Further, in preferred embodiments of the present invention, the first heating speed be 1~2 DEG C/min, described second
Heating rate is 3~5 DEG C/min.
Further, in preferred embodiments of the present invention, the nitridation carbon matrix precursor is selected from urea, cyanamide, double cyanogen
One of amine and melamine are a variety of.
Further, in preferred embodiments of the present invention, first solvent is ethanol water.
Further, in preferred embodiments of the present invention, in the mixed liquor, the concentration of the sodium bicarbonate is 0.1
~0.2g/ml, the volumetric concentration of the isopropanol are 8~12%v/v, and the concentration of the polyvinylpyrrolidone is 4~6mg/
ml。
Further, in preferred embodiments of the present invention, second solvent is selected from dehydrated alcohol, polyethylene glycol and pyrrole
It is one or more of in pyridine.
Further, in preferred embodiments of the present invention, CdIn2S4/g-C3N4It is described in mixture preparation step
CdIn2S4With the g-C3N4Mass ratio be 0.3~0.8:1.
Further, in preferred embodiments of the present invention, BiVO4@CdIn2S4/g-C3N4It is described in preparation step
CdIn2S4/g-C3N4Additional amount of the mixture in the third solution is 2~12mg/ml.
The present invention also proposes a kind of BiVO4@CdIn2S4/g-C3N4Visible light responsive photocatalyst, according to above-mentioned preparation side
Method is made.
The BiVO of the embodiment of the present invention4@CdIn2S4/g-C3N4Visible light responsive photocatalyst and preparation method thereof it is beneficial
Effect is:
Few lamella g-C3N4It is a kind of polymer semiconductor's visible-light photocatalyst, structure and photocatalytic hydrogen production by water decomposition
It can stablize, catalyst is reusable, environmentally friendly.Few lamellar structure provides biggish specific surface for photocatalysis hydrolytic hydrogen production
Product, quantum yield are high.Monolithic or few lamella CdIn2S4When preparation, by by reaction product containing sodium bicarbonate, isopropanol and
It is heated at reflux in the aqueous solution of polyvinylpyrrolidone, Effective Regulation CdIn2S4Nucleation and growth, to form monolithic
The metal sulfide of layer or few lamella, avoids the formation of block structure, improves hydrogen generation efficiency.
In addition, BiVO4Band gap is 2.40eV, and valence band and conduction band positions are located at+2.70eV and+0.30 eV, photoproduction
Electron-hole pair has stronger redox ability.Pass through In-situ reaction BiVO4And CdIn2S4/g-C3N4Mixture, can
The partial size for regulating and controlling product constructs hetero-junctions compound system, improves the ability of transmission charge, and photogenerated charge separative efficiency is high, extends
The photo-generated carrier service life, so that photochemical catalyst has good Photocatalyzed Hydrogen Production effect.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to the BiVO of the embodiment of the present invention4@CdIn2S4/g-C3N4Visible light responsive photocatalyst and preparation method thereof
It is specifically described.
A kind of present invention provided in an embodiment of the present invention proposes a kind of BiVO4@CdIn2S4/g-C3N4Visible light-responded light is urged
The preparation method of agent, comprising the following steps:
S1, few lamella g-C3N4Preparation: calcining is carried out to nitridation carbon matrix precursor and obtains few lamella g-C3N4。
Further, in the step, the step of calcining to nitridation carbon matrix precursor are as follows: be warming up to the first heating speed
500~550 DEG C, 1~3h is calcined, after cooling, grinding obtains the first calcined material to obtained calcined product;Then with the second heating
First calcined material is warming up to 500~550 DEG C by speed, calcines 1~3h, and obtained calcined product after cooling, is ground
To few lamella g-C3N4。
Further, in the step, the first heating speed is 1~2 DEG C/min;Second heating rate be 3~5 DEG C/
min.First be warming up to 500~550 DEG C in lower heating rate and calcined, calcined product after supercooling, milled processed, then
500~550 DEG C are warming up to higher heating rate to be calcined again, it can be to g-C3N4Pattern regulated and controled, help and receive
The driving of rice chip architecture improves hydrogen generation efficiency conducive to the separation and transfer of photo-generated carrier.
Further, in the step, one of carbon matrix precursor in urea, cyanamide, dicyandiamide and melamine is nitrogenized
Kind is a variety of.It is further preferable that nitridation carbon matrix precursor selects urea.
Further, in the step, after calcined product is cooling, using ratio of grinding media to material 1:7 zirconia ball to calcined product into
Row grinding, milling time 0.5-1h.It is ground after calcining, the surface stress of product can be removed, particle passes through repeatedly
Broken-cold welding-shattering process forms few lamellar structure, is conducive to the quick transmission of charge and answers conducive to other compositions
It closes.
S2, monolithic or few lamella CdIn2S4Preparation: by divalent cadmium salt, trivalent indium salts and thioacetamide according to a mole score
It is not dissolved in the first solvent, then mixes, heat 22-30h under the conditions of 140~200 DEG C, separated, washed, dried,
Reaction product is obtained after grinding;The reaction product is placed in mixed liquor and is heated to reflux 1~3h, obtains monolithic or few lamella
CdIn2S4, wherein the mixed liquor is the aqueous solution containing sodium bicarbonate, isopropanol and polyvinylpyrrolidone.
Further, in the step, divalent cadmium salt selects cadmium acetate, and trivalent indium salts select inidum chloride, according to Cd:In:S object
The amount ratio of matter is that 1:2:4 weighs cadmium acetate, inidum chloride, thioacetamide respectively.
Further, in the step, the first solvent is ethanol water.Under alcoholic solution effect, available thin layer is received
Rice chip architecture, nanometer sheet are conducive to the separation and transfer of photo-generated carrier, improve hydrogen generation efficiency.
Further, in the step, in mixed liquor, the concentration of sodium bicarbonate is 0.1~0.2g/ml, the volume of isopropanol
Concentration is 8~12%v/v, and the concentration of polyvinylpyrrolidone is 4~6mg/ml.
Further, in the step, the solid-liquid ratio of reaction product and mixed liquor is 1~10mg/ml.
Further, in the step, the temperature that reaction product is heated to reflux in mixed liquor is 80~110 DEG C.Passing through will
Reaction product is heated to reflux in mixed liquor, and realization regulates and controls the sample topography and dispersion performance of product, avoids shape
It is grown at the aggregation of particle, obtained CdIn2S4For monolithic layer or few lamellar structure, specific surface area is bigger, is capable of providing more
Reactivity site.
S3, CdIn2S4/g-C3N4Mixture preparation: by the g-C3N4With the CdIn2S4It mixes, steams in the second solvent
Second solvent is done, CdIn is then dried to obtain2S4/g-C3N4Mixture.
Further, in the step, the second solvent is one or more of in dehydrated alcohol, polyethylene glycol and pyridine.More
For preferably, the second solvent is selected from dehydrated alcohol.
Further, in the step, it is evaporated the second solvent using Rotary Evaporators, rotating evaporation temperature is 40~50 DEG C,
6h is dried under the conditions of 60 DEG C after being evaporated, obtains compound few lamella CdIn2S4/g-C3N4Mixture.
Further, in the step, CdIn2S4And g-C3N4Mass ratio be 0.3~0.8:1, it is further preferable that
CdIn2S4And g-C3N4Mass ratio be 0.6:1.
By in ethanol solution rotary evaporation to CdIn2S4And g-C3N4Carry out compound, process is simple, solvent can return
It receives, and reaction condition is mild.
S4, BiVO4@CdIn2S4/g-C3N4Preparation: trivalent bismuth salt being dissolved in acetic acid solution and obtains the first solution, will be inclined
Ammonium vanadate, which is dissolved in ammonia spirit, obtains the second solution, obtains after first solution and second solution are slowly mixed together
Third solution;The pH to 7~8 of the third solution is adjusted, the CdIn is added after stirring 30~60min2S4/g-C3N4Mixing
Object after ultrasonic disperse, reacts 2-4h under the conditions of 140~200 DEG C, is cooled and separated, washs, drying and grinding obtains
BiVO4@CdIn2S4/g-C3N4Visible light responsive photocatalyst.
Further, in the step, trivalent bismuth salt is selected from one of bismuth nitrate, bismuth chloride, bismuth acetate and bismuth citrate
Or it is a variety of.It is further preferable that trivalent bismuth salt is bismuth nitrate.Acetic acid solution is the mixed solution of the acetic acid that volume ratio is 1:1 and water.
Concentration of the bismuth nitrate in acetic acid solution is 2~5mol/L.
Further, in the step, ammonia spirit is the mixing of ammonium hydroxide (containing ammonia 25wt%) and water that volume ratio is 3:1
Solution.Concentration of the ammonium metavanadate in ammonia spirit is 2~5mol/L.
Further, in the step, with the pH to 7~8 of ammonium hydroxide section third solution, specifically, adjustment process are as follows: adjusting
20ml ammonium hydroxide is first added in the process, then ammonium hydroxide is slowly added dropwise, until pH is 7~8.
Further, in the step, CdIn2S4/g-C3N4Additional amount of the mixture in third solution is 2~12mg/
Ml, it is further preferable that CdIn2S4/g-C3N4Additional amount of the mixture in third solution is 8~10mg/ml.
Further, in the step, the condition of ultrasonic disperse is 1~2h of ultrasonic disperse under the power of 400~600W.?
Under ultrasonic wave effect, the size of product can be effectively reduced, and product is degraded into nano-lamellar structure.
BiVO4Band gap is 2.40eV, and valence band and conduction band positions are located at+2.70eV and+0.30eV, light induced electron-
Hole is to stronger redox ability.By hydro-thermal reaction, in CdIn2S4/g-C3N4The surface of mixture coats
BiVO4, form BiVO4@CdIn2S4/g-C3N4Core-shell structure, thus the electric charge transfer between being more advantageous to interface, it is suppressed that photoproduction
Carrier it is compound, improve photocatalytic activity.
The embodiment of the present invention also proposes a kind of BiVO4@CdIn2S4/g-C3N4Visible light responsive photocatalyst, according to above-mentioned
Preparation method is made.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of BiVO provided in this embodiment4@CdIn2S4/g-C3N4Visible light responsive photocatalyst, according to following steps
It is made:
(1) it takes 10g urea to be placed in alumina crucible with a lid, is placed in Muffle furnace and is heated up with the speed of 1 DEG C/min
To 550 DEG C, 2h is kept the temperature, cooled to room temperature takes out grinding 0.5h, obtains sample and place into alumina crucible with a lid
In, it is placed in Muffle furnace and is warming up to 500 DEG C with the speed of 4 DEG C/min, keep the temperature 3h, cooled to room temperature takes out grinding
0.5h obtains few lamella g-C3N4Powder.
It (2) at room temperature, is that 1:2:4 weighs cadmium acetate, inidum chloride, thioacetyl by Cd:In:S the mass ratio of the material
Amine is dissolved separately in the ethanol water of 30ml, and magnetic agitation 30min is transferred in polytetrafluoroethylene bushing, is placed into stainless
In steel reaction kettle, heating is reacted for 24 hours at 180 DEG C.After reaction, it after 1000rpm is centrifuged 30min, is first washed with deionized water
It washs 3 times, then is washed three times with dehydrated alcohol, after 60 DEG C dry 12 hours, grinding obtains reaction product A.
(3) the reaction product A in step (2) is added to and is connected with condenser pipe and the 500ml three-necked flask with thermometer
Reflux unit in, be added 10g sodium bicarbonate, 10ml isopropanol, 0.5g polyvinylpyrrolidone, 100ml deionized water, be placed on
It is heated to reflux 2h on electric heating cover with magnetic agitation, filters, is first washed with deionized 3 times, then wash three with dehydrated alcohol
It is secondary, obtain monolithic or few lamella CdIn2S4Powder.
(4) CdIn that will be obtained2S4And g-C3N4Sample is blended in 50ml dehydrated alcohol according to mass ratio 0.6:1, true
It is evaporated in empty Rotary Evaporators, is placed on 60 DEG C of drying 6h in drying box, obtain compound few lamella CdIn2S4/g-C3N4Mixture.
(5) V by volume(acetic acid): V(water)=1:1 prepares acetic acid solution, accurately weighs bismuth nitrate 1g and is dissolved in acetic acid solution,
Magnetic agitation 20min dissolves bismuth nitrate sufficiently.V by volume(ammonium hydroxide): V(water)=3:1 prepares ammonia spirit, accurately weighs inclined vanadium
Sour ammonium 0.2g is dissolved in ammonia spirit, and magnetic agitation 20min is completely dissolved ammonium metavanadate.
(6) after being slowly mixed together two kinds of solution in step (5), magnetic agitation 1h adjusts pH=7 with ammonium hydroxide and (is adjusting
20mL ammonium hydroxide is first added in the process, then is slowly added dropwise, until pH is 7), CdIn to be added after continuing to stir 0.5h2S4/g-C3N4
Mixture, ultrasonic disperse 1h are transferred in the autoclave container containing polytetrafluoroethyllining lining, 3h are reacted at 160 DEG C, instead
It should complete, sample is cooled to room temperature and is taken out, be put into centrifuge tube centrifugation, wash centrifugation three repeatedly with distilled water and dehydrated alcohol
It is secondary, BiVO is ground to obtain after 60 DEG C of baking 18h4@CdIn2S4/g-C3N4Visible light responsive photocatalyst sample.
Embodiment 2
A kind of BiVO provided in this embodiment4@CdIn2S4/g-C3N4Visible light responsive photocatalyst, with embodiment 1
Difference place is:
Step (1) are as follows: take 10g urea to be placed in alumina crucible with a lid, be placed in Muffle furnace with the speed of 1 DEG C/min
Degree is warming up to 550 DEG C, keeps the temperature 5h, and cooled to room temperature takes out grinding 1h and obtains g-C3N4Powder.
Comparative example 1
This comparative example provides a kind of CdIn2S4/g-C3N4Visible light responsive photocatalyst, for according to the method for embodiment 1
The CdIn of acquisition2S4/g-C3N4Mixture.
Comparative example 2
This comparative example provides a kind of visible light responsive photocatalyst, is obtained according to following steps:
(1) few lamella g-C is obtained according to (1) the step of embodiment 13N4Powder.
(2) reaction product A is obtained according to (2) the step of embodiment 1.
(3) the reaction product A and g-C that will be obtained3N4Sample is blended in 50ml dehydrated alcohol, in vacuum rotary evaporator
In be evaporated, be placed on 60 DEG C of drying 6h in drying box, obtain compound few lamella CdIn2S4/g-C3N4Mixture.
(4) BiVO is obtained according to embodiment step (5) and step (6)4@CdIn2S4/g-C3N4Visible light responsive photocatalyst
Sample.
Comparative example 3
This comparative example provides a kind of visible light responsive photocatalyst, is obtained according to following steps:
(1) few lamella g-C is obtained according to (1) the step of embodiment 13N4Powder.
(2) few lamella CdIn is obtained according to (2) the step of embodiment 1 and step (3)2S4Powder.
(3) V by volume(acetic acid): V(water)=1:1 prepares acetic acid solution, accurately weighs bismuth nitrate 1g and is dissolved in acetic acid solution,
Magnetic agitation 20min dissolves bismuth nitrate sufficiently.V by volume(ammonium hydroxide): V(water)=3:1 prepares ammonia spirit, accurately weighs inclined vanadium
Sour ammonium 0.2g is dissolved in ammonia spirit, and magnetic agitation 20min is completely dissolved ammonium metavanadate.
(4) after being slowly mixed together two kinds of solution in step (3), magnetic agitation 1h adjusts pH=7 with ammonium hydroxide and (is adjusting
20mL ammonium hydroxide is first added in the process, then is slowly added dropwise, until pH is that 7), addition step (1) obtains after continuing stirring 0.5h
Few lamella g-C3N4Few lamella CdIn that powder and step (2) obtain2S4Powder, ultrasonic disperse 1h, is transferred to containing polytetrafluoroethylene (PTFE)
In the autoclave container of liner, react 3h at 160 DEG C, reaction is completed, and sample is cooled to room temperature and is taken out, be put into from
The centrifugation of heart pipe washs centrifugation three times with distilled water and dehydrated alcohol repeatedly, grinds to obtain BiVO after 60 DEG C of baking 18h4@CdIn2S4/
g-C3N4Visible light responsive photocatalyst sample.
The measurement of test example H2-producing capacity
Light-catalyzed reaction, light-catalyzed reaction are carried out using product made from embodiment 1-2 and comparative example 1-3 as catalyst
It is carried out in 500mL Pyrex reactor assembly, temperature is 25 DEG C.The aqueous solution containing methanol is added in photochemical catalyst, as
Reaction medium.It will be put into Photoreactor in reaction medium.After reaction system leads to argon gas 30min, with the xenon lamp of 300W (equipped with filter
Mating plate) with visible light (420 < λ < 800nm) system 4h is irradiated, which is looped around the side of Photoreactor.Reactor outer circulation
It is passed through condensed water.The photocatalysis effect of five kinds of samples is as shown in table 1:
Table 1
Sample |
Average hydrogen-producing speed (using for the first time) |
Average hydrogen-producing speed (using after 20 times) |
Embodiment 1 |
519.2μmol/(h·g) |
488.0μmol/(h·g) |
Embodiment 2 |
457.4μmol/(h·g) |
416.2μmol/(h·g) |
Comparative example 1 |
361.3μmol/(h·g) |
130.1μmol/(h·g) |
Comparative example 2 |
422.5μmol/(h·g) |
219.7μmol/(h·g) |
Comparative example 3 |
417.6μmol/(h·g) |
186.2μmol/(h·g) |
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.