CN104248977B - Method and the purposes of composite photo-catalyst prepared by a kind of photosensitizer - Google Patents
Method and the purposes of composite photo-catalyst prepared by a kind of photosensitizer Download PDFInfo
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- CN104248977B CN104248977B CN201410439228.0A CN201410439228A CN104248977B CN 104248977 B CN104248977 B CN 104248977B CN 201410439228 A CN201410439228 A CN 201410439228A CN 104248977 B CN104248977 B CN 104248977B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a kind of photosensitizer and prepare method and the purposes of composite photo-catalyst, the photosensitizer in the method is N, N ' dimethyl amidopBenzyl imidodicarbonic diamide, with platinum load organic semiconductor photocatalyst class graphite type carbon nitride as matrix, use supermolecule assemble method absorption photosensitizer N, N ' dimethyl amidopBenzyl imidodicarbonic diamide and build, the composite photo-catalyst obtained by the method for the invention be dispersed in electron donor sacrifice reagent triethanolamine aqueous solution in, may be implemented in the purposes in terms of visible light responsible photocatalytic hydrogen production by water decomposition.Photosensitizer novel structure used by the present invention, synthesize and productivity height, photochemical stable, visible light-responded wide ranges, raw material are easy to get and can be recycled.This composite photo-catalyst has photochemistry and the heat stability of excellence, and good is visible light-responded, and preparation method is simple, abundant raw material source, can be used for the solar energy photocatalytic hydrogen production by water decomposition that low cost is practical.
Description
Technical field
The invention belongs to materials science field, prepare method and the use of composite photo-catalyst particularly to a kind of photosensitizer
On the way.
Background technology
Hydrogen energy source is efficient green energy resource, the cheapest efficient large-scale production be restriction its application one crucial because of
Element.Current industrial numerous hydrogen producing technology, such as Fossil fuel hydrogen manufacturing, water electrolysis hydrogen production, thermal decomposition water hydrogen manufacturing and biological system
Hydrogen etc., generally exist severe reaction conditions, power consumption is big, by-product is many, environmental pollution or high in cost of production not enough, therefore, closely
In decades, be devoted to consistent with industrial quarters of academia is found and develops new hydrogen producing technology.From semiconductor light in 1972
Since catalysis technique finds, utilize the direct photochemical catalyzing of inexhaustible solar energy become environmental protection cheap, the simplest and
The most promising hydrogen manufacturing approach.The core of this technology be to obtain cheap, light quantum conversion ratio height, photochemical stable, can
See the semiconductor light-catalyst that photoresponse is good, design efficient photocatalysis system and set up relevant theory.
Traditional semiconductor light-catalyst mostly is inorganic semiconductor nano-particle, and the most most important and most widely used is dioxy
Change titanium, but its energy gap is relatively big (about 3.2eV), can only respond ultraviolet light, and ultraviolet light only accounts for solar energy gross energy
About 4%, and easily assemble and adsorbing contaminant during using, cause hydraulic performance decline, etc. these all significantly limit
It is in the application in photocatalysis hydrogen production field.And other has the inorganic semiconductor such as cadmium sulfide of narrow band gap, then there is serious light
Etching problem, i.e. light stability are poor, auto-degradation easily occurs under illumination, is unsuitable for actual application.2009, novel
Organic semiconductor class graphite type carbon nitride be used successfully to visible light-responded hydrogen production by water decomposition as photocatalyst.Class graphite mould nitrogen
Changing carbon is the nonmetal semiconducting organic polymer that a kind of energy gap is about 2.7eV, has visible light-responded, and heat is steady
Qualitative good with chemical stability, relative to inorganic semiconductor, raw material sources are more extensively cheap, and structural modification is easier,
Therefore show the advantage of uniqueness in photocatalytic hydrogen production by water decomposition field, have become as what academic circles at present and industrial circle were paid close attention to
One focus.But the simple specific surface area of class graphite type carbon nitride own is less, the narrowest to the response range of visible ray,
The same with inorganic semiconductor nano-particle, it is faced with photo-generate electron-hole to compound fast, photogenerated charge separation and efficiency of transmission
The most high defect, limits the raising of its photocatalysis hydrogen production efficiency.At present, typically adjusted by copolymerization, element doping, pattern
It is modified by the means such as control, but these means the most largely change the structure of class graphite type carbon nitride itself,
And need the control measures of secondary clacining, strong acid and strong base or complexity, increase the difficulty of its popularization and application and industrialized production.
Dye sensitization as the simple method of modifying of one, can by introducing photosensitizer, and semiconductor light-catalyst combine build compound
Photocatalyst, is greatly improved the spectral response range of photocatalyst, thus realizes visible light-responded photocatalytic hydrogen production by water decomposition.
Common photosensitizer includes rhodamine B, phthalocyanine, coumarin, chlorophyll, eosin, Cyclometalated iridium, bipyridyl ruthenium etc., its
In the preferable photosensitizer generally acknowledged at present be Polypyridine ruthenium compounds.But the light stability of most of photosensitizer is poor,
Photocatalytic process exists the decomposition of self, and the absorption that dye molecule is on semiconductor grain surface exists easy to fall off, defect
A series of defects such as many, carrier transport is the most smooth.As must be located further with semiconductor light-catalyst active adsorption and combination
Reason, and this is it is generally required to process through complicated high temperature high heat, concentrated acid concentrated base, functional group structural modification etc..By modifying acid
Base or phosphate etc., can make Polypyridine ruthenium compounds can preferably be combined in conductor oxidate surface, and illumination excites down
Injecting electrons into the conduction band of semiconductor light-catalyst efficiently, rear light induced electron is transferred to the gold of semiconductor grain area load
Belong to promoter (platinum etc.), final reductive water hydrogen making, but this type of photocatalyst contains rare metal, and system itself
Standby difficulty is big, easily causes environmental pollution, is unsuitable for large-scale promotion application.
To sum up, find cheap and easy to get, photochemical stable, visible light-responded good and efficient dyestuff photosensitizer, and with partly lead
Body nano-particle combines and builds novel composite photo-catalyst, it appears the most urgent and necessary.
Diimide compounds is that minority has height photochemistry and the organic dyestuff photosensitizer of thermal stability concurrently, is also
One of important n-type molecule organic semiconductor, has been successfully applied to DSSC and bulk heterojunction too the most
The fields such as sun energy battery, life-time service does not produce photoetch, and synthetic route is simple, and raw material is easy to get, and photoelectric respone is good,
Can absorb visible ray, by structure regulating, absorption region can be expanded further to ultrared.It addition, the LUMO of itself
Energy level and TiO2With the hydrogen-evolution overpotential coupling of the semiconductor light-catalyst such as class graphite type carbon nitride and photochemical catalyzing, and have
Good redox property.But imidodicarbonic diamide molecule itself is electrophilic structure, photogenerated charge produces, separates and turn
Shifting efficiency is low, when additionally it is as photosensitizer, it is also desirable to concentrated acid concentrated base or High Temperature High Pressure etc. process, and limit it at the sun
The application of photosemiconductor photocatalysis hydrogen production.Therefore by MOLECULE DESIGN, imidodicarbonic diamide is carried out functionalization, with development of new
Efficient photosensitizer, selects suitable photocatalyst matrix material and to develop new composite photo-catalyst preparation method the most urgent
Cut.
Summary of the invention
It is an object of the invention to, it is provided that a kind of photosensitizer prepares method and the purposes of composite photo-catalyst, the light in the method
Quick dose is N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide, uses the organic semiconductor photocatalyst class stone of platinum load
Ink type carbonitride is matrix, the photosensitizer N, N '-dimethyl amido-p-that the method absorption present invention assembled with supermolecule provides
The mode of benzyl-imidodicarbonic diamide builds, and the composite photo-catalyst obtained by the method for the invention is dispersed in electron donor
Type is sacrificed in the aqueous solution of reagent (triethanolamine), may be implemented in the purposes of visible light responsible photocatalytic hydrogen production by water decomposition.
The method that composite photo-catalyst prepared by a kind of photosensitizer of the present invention, the photosensitizer in the method is N, N '-two
Methylamino-p-benzyl-imidodicarbonic diamide, concrete operations follow these steps to carry out:
A, platinum/class graphite type carbon nitride powder is joined containing N, the three of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide
In chloromethanes solution, ultrasonic disperse is after 5 minutes, and under dark condition, in 20 DEG C of water-baths of constant temperature, magnetic agitation 6-12 is little
Time, obtain mixed solution system；
B, mixed solution system step a obtained are slowly injected into methanol, continue stirring 6-12 hour, stand 30 points
Sucking filtration after clock, again with methanol is washed, and is dried 6 hours, i.e. obtains composite photo-catalyst N in 100 DEG C of air dry ovens of temperature,
N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride.
Platinum/class graphite type carbon nitride and N in step a, the weight ratio of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide is
200-400∶1。
In step a, chloroform soln concentration is 10-25mg/L.
In step b, the addition of methanol is 4-5 times of volume of chloroform.
The composite catalyst that described method obtains is in the purposes preparing visible light responsible photocatalytic decomposition water hydrogen making.
The method that composite photo-catalyst prepared by a kind of photosensitizer of the present invention, the photosensitizer in the method is N, N '-two
Methylamino-p-benzyl-imidodicarbonic diamide, its structural formula is:
Method and the purposes of composite photo-catalyst prepared by a kind of photosensitizer of the present invention, in the method photosensitizer be N, N '-
Dimethyl amido-p-benzyl-imidodicarbonic diamide, it is sub-to be that one has two acyls of electron donor-electron acceptor (D-A) structure
Amine derivative, this photosensitizer prepared by following simple route:
With 3,4,9,10-tetracarboxylic anhydrides, N, N '-dimethyl amido-p-benzylamine and zinc acetate are raw material, temperature 120 DEG C
Under in melted imidazoles react 4-5 hour, then in dehydrated alcohol and 2M aqueous hydrochloric acid solution disperse 12-24 hour, take out
Filter washing, is finally dried to obtain N, and N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder, productivity is up to about 90%.
Composite photo-catalyst of the present invention is N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite mould
Carbonitride, wherein N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide is photosensitizer, and platinum/class graphite type carbon nitride is
Matrix.
The method that composite photo-catalyst prepared by a kind of photosensitizer of the present invention, composite photo-catalyst matrix used material platinum/
The preparation method of class graphite type carbon nitride is:
Weigh tripolycyanamide 5g, insert in porcelain crucible after grinding, spread even, put into temperature 600 DEG C calcining 4 in Muffle furnace little
Time, cool down afterwards, grind and obtain class graphite type carbon nitride powder；
25mg class graphite type carbon nitride powder is joined the reactor filling the aqueous solution that 100mL concentration is 10% methanol
In, ultrasonic disperse 10 minutes, add the chloroplatinic acid aqueous solution of 3.33mL 0.1g/L, magnetic agitation, and use 500
Watt high voltage mercury lamp radiation 1-2 hour, sucking filtration, temperature 100 DEG C is vacuum dried 6-12 hour, obtains platinum/class graphite mould nitrogen
Change carbon dust.
The purposes of the described composite photo-catalyst of the present invention is: the composite photo-catalyst that will be obtained by the method for the invention
The powder of N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride, is scattered in 10% 3 ethanol
In the aqueous solution of amine, to configure the xenon lamp of 420 nanometer edge filters as visible light source, it is achieved visible light-responded light is urged
Changing the purposes of decomposition water hydrogen making, produced gas can use gas chromatogram survey on-line testing and calculate content.
The advantage of the method and purposes that composite photo-catalyst prepared by a kind of photosensitizer of the present invention is:
Organic semiconductor compound N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide has calorifics and the photochemistry of excellence
Stability, outstanding visible absorption performance and synthetic route are easy, raw material is easy to get, product purity and productivity high, itself
Lumo energy and the semiconductor light-catalyst such as titanium dioxide and class graphite type carbon nitride so that the liberation of hydrogen electricity of photochemical catalyzing
Position matches；N, imidodicarbonic diamide body construction (A) is not only had by N '-dimethyl amido-p-benzyl substituent (D)
Supplied for electronic effect, forms the conjugated molecule of D-A type, is allowed to have excellent oxidoreduction and photogenerated charge and transmittability,
Bridging methyl between D and A group promotes the separation of photogenerated charge simultaneously, decreases the recombination probability of photo-generate electron-hole；
With cheap raw material tripolycyanamide as raw material, by calcining preparation class graphite type carbon nitride in atmosphere, simple, suitably
Prepared by scale, and structure exists certain defective bit, and edge of materials contains the amino of residual, can with carbonyl
Imidodicarbonic diamide effect is adsorbed；N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide molecule can be by the work of π-π stacking
With, the solution of chloroform and methanol is formed orderly supramolecular aggregation, further promotes itself and platinum/class graphite
The cladding of type carbonitride and combination；Chloroplatinic acid photo-reduction load class graphite type carbon nitride prepares platinum/class graphite type carbon nitride, N,
N '-dimethyl amido-p-benzyl-imidodicarbonic diamide sensitization platinum/class graphite type carbon nitride prepare composite photo-catalyst, compound
The visible light-responded hydrogen production by water decomposition reaction of photocatalyst is carried out the most under magnetic stirring, and these processes can be amplified simply
Scale, and operating condition is simple, is suitable to the needs of actual application；It addition, photosensitizer different from the past, of the present invention
N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide is recyclable as photosensitizer and reuses.This complex light final
Catalyst can realize its purposes in terms of visible light-responded water decomposition hydrogen manufacturing, and hydrogen manufacturing performance is stable, reclaims easily, makes
By low cost, practical for solar energy photocatalytic hydrogen production by water decomposition provides an approach.
Accompanying drawing explanation
Fig. 1 is photosensitizer N of the present invention, the infared spectrum of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder.
Fig. 2 is the XRD figure spectrum of composite photo-catalyst matrix powder of the present invention, and wherein 1 is class graphite type carbon nitride, 2
For platinum/class graphite type carbon nitride.
Fig. 3 is the uv drs absorption spectrum of material powder of the present invention, and wherein 1 is class graphite type carbon nitride, and 2 are
Platinum/class graphite type carbon nitride, 3 is N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride.
Fig. 4 is composite photo-catalyst N of the present invention, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite
The stereoscan photograph of type carbonitride.
Fig. 5 be composite photo-catalyst of the present invention under visible ray (＞ 420 nanometer), at 10% triethanolamine aqueous solution
Middle photocatalysis Decomposition Aquatic product hydrogen figure, wherein 1 is platinum/class graphite type carbon nitride, and 2 is N, N '-dimethyl amido-p-benzyl-
Imidodicarbonic diamide/platinum/class graphite type carbon nitride.
Detailed description of the invention
Below by the drawings and specific embodiments, the present invention is further described:
Embodiment 1
Photosensitizer N, the synthesis of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide:
Weigh 784.6mg 3,4,9,10-tetracarboxylic anhydrides, 901.4mg N, N '-dimethyl amido-p-benzylamine, 20g
Imidazoles and 18mg zinc acetate join in 100mL three neck round bottom, oil bath 120 DEG C, and magnetic agitation is reacted 5 hours,
Rear cooling is also poured in the 500mL single necked round bottom flask containing 100mL dehydrated alcohol, after magnetic agitation half an hour, adds
300mL 2M aqueous hydrochloric acid solution, magnetic agitation 12 hours, rear sucking filtration, to wash, methanol is washed, and end temperature 80 DEG C is dried
12 hours, obtain N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder；
The preparation of composite photo-catalyst matrix platinum/class graphite type carbon nitride:
Weigh tripolycyanamide 5g, insert in porcelain crucible after grinding, spread even, put into temperature 600 DEG C calcining 4 in Muffle furnace little
Time, cool down afterwards, grind and obtain class graphite type carbon nitride powder；
25mg class graphite type carbon nitride powder is joined the reactor filling the aqueous solution that 100mL concentration is 10% methanol
In, ultrasonic disperse 10 minutes, add the chloroplatinic acid aqueous solution of 3.33mL 100mg/L, limit magnetic agitation snare drum bubble 10
Minute nitrogen, rear uses 500 watts of high voltage mercury lamp radiations 1 hour, sucking filtration, and temperature 100 DEG C is vacuum dried 6 hours,
To platinum/class graphite type carbon nitride powder；
The preparation of composite photo-catalyst N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride:
The platinum prepared by 25mg/class graphite type carbon nitride powder joins containing N, N '-dimethyl amido-p-benzyl-two
Imido concentration is in 10mg/L chloroform soln, platinum/class graphite type carbon nitride and N, N '-dimethyl amido-p-
The weight ratio of benzyl-imidodicarbonic diamide is 200: 1, and ultrasonic disperse is after 5 minutes, under dark condition, and 20 DEG C of water of constant temperature
In bath, magnetic agitation 12 hours, obtain mixed solution system；
Being slowly injected into methanol in the mixed solution system that will obtain, the addition of methanol is 4 times of volumes of chloroform, continues
Magnetic agitation 6 hours, sucking filtration after standing 30 minutes, then wash 3 times with 10mL methanol, 100 DEG C of forced air dryings of temperature
Case is dried 6 hours, i.e. obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride powder
End sample.
Embodiment 2
Photosensitizer N, the synthesis of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide:
Weigh 784.6mg 3,4,9,10-tetracarboxylic anhydrides, 901.4mg N, N '-dimethyl amido-p-benzylamine, 20g
Imidazoles and 18mg zinc acetate join in 100mL three neck round bottom, oil bath temperature 120 DEG C, magnetic agitation reaction 5
Hour, cool down afterwards and be poured in the 500mL single necked round bottom flask containing 100mL dehydrated alcohol, after magnetic agitation half an hour,
Adding 300mL 2M aqueous hydrochloric acid solution, magnetic agitation 12 hours, rear sucking filtration, wash, methanol is washed, end temperature 80 DEG C
It is dried 12 hours, obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder；
The preparation of composite photo-catalyst matrix platinum/class graphite type carbon nitride:
Weigh tripolycyanamide 5g, insert in porcelain crucible after grinding, spread even, put into temperature 600 DEG C calcining 4 in Muffle furnace little
Time, cool down afterwards, grind and obtain class graphite type carbon nitride powder；
25mg class graphite type carbon nitride powder is joined the reactor filling the aqueous solution that 100mL concentration is 10% methanol
In, ultrasonic disperse 10 minutes, add the chloroplatinic acid aqueous solution of 3.33mL 100mg/L, limit magnetic agitation snare drum bubble 10
Minute nitrogen, rear uses 500 watts of high voltage mercury lamp radiations 1 hour, sucking filtration, and temperature 100 DEG C is vacuum dried 6 hours,
To platinum/class graphite type carbon nitride powder；
The preparation of composite photo-catalyst N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride:
The platinum prepared by 25mg/class graphite type carbon nitride powder joins containing N, N '-dimethyl amido-p-benzyl-two
Imido concentration is in 12.5mg/L chloroform soln, platinum/class graphite type carbon nitride and N, N '-dimethyl amido
The weight ratio of-p-benzyl-imidodicarbonic diamide is 300: 1, and ultrasonic disperse is after 5 minutes, under dark condition, and constant temperature 20 DEG C
In water-bath, magnetic agitation 10 hours, obtain mixed solution system；
Being slowly injected into 10mL methanol in the mixed solution system that will obtain, the addition of methanol is 5 times of volumes of chloroform,
Continue magnetic agitation 8 hours, sucking filtration after standing 30 minutes, then wash 3 times with 10mL methanol, 100 DEG C of air blast of temperature
Drying baker is dried 6 hours, i.e. obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite mould nitridation
Carbon dust sample.
Embodiment 3
Photosensitizer N, the synthesis of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide:
Weigh 784.6mg 3,4,9,10-tetracarboxylic anhydrides, 901.4mg N, N '-dimethyl amido-p-benzylamine, 20g
Imidazoles and 18mg zinc acetate join in 100mL three neck round bottom, oil bath temperature 120 DEG C, magnetic agitation reaction 5
Hour, cool down afterwards and be poured in the 500mL single necked round bottom flask containing 100mL dehydrated alcohol, after magnetic agitation half an hour,
Adding 300mL 2M aqueous hydrochloric acid solution, magnetic agitation 12 hours, rear sucking filtration, wash, methanol is washed, end temperature 80 DEG C
It is dried 12 hours, obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder；
The preparation of composite photo-catalyst matrix platinum/class graphite type carbon nitride:
Weigh tripolycyanamide 5g, insert in porcelain crucible after grinding, spread even, put into temperature 600 DEG C calcining 4 in Muffle furnace little
Time, cool down afterwards, grind and obtain class graphite type carbon nitride powder；
25mg class graphite type carbon nitride powder is joined the reactor filling the aqueous solution that 100mL concentration is 10% methanol
In, ultrasonic disperse 10 minutes, add the chloroplatinic acid aqueous solution of 3.33mL 100mg/L, limit magnetic agitation snare drum bubble 10
Minute nitrogen, rear uses 500 watts of high voltage mercury lamp radiations 1 hour, sucking filtration, and temperature 100 DEG C is vacuum dried 6 hours,
To platinum/class graphite type carbon nitride powder；
The preparation of composite photo-catalyst N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride:
The platinum prepared by 25mg/class graphite type carbon nitride powder joins containing N, N '-dimethyl amido-p-benzyl-two
Imido concentration is in 20mg/L chloroform soln, platinum/class graphite type carbon nitride and N, N '-dimethyl amido-p-
The weight ratio of benzyl-imidodicarbonic diamide is 400: 1, and ultrasonic disperse is after 5 minutes, under dark condition, and 20 DEG C of water of constant temperature
In bath, magnetic agitation 6 hours, obtain mixed solution system；
Being slowly injected into methanol in the mixed solution system that will obtain, the addition of methanol is 4 times of volumes of chloroform, continues magnetic
Power stirs 10 hours, sucking filtration after standing 30 minutes, then washs 3 times with 10mL methanol, 100 DEG C of forced air dryings of temperature
Case is dried 6 hours, i.e. obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride powder
End sample.
Embodiment 4
Photosensitizer N, the synthesis of N '-dimethyl amido-p-benzyl-imidodicarbonic diamide:
Weigh 784.6mg 3,4,9,10-tetracarboxylic anhydrides, 901.4mg N, N '-dimethyl amido-p-benzylamine, 20g
Imidazoles and 18mg zinc acetate join in 100mL three neck round bottom, oil bath temperature 120 DEG C, magnetic agitation reaction 5
Hour, cool down afterwards and be poured in the 500mL single necked round bottom flask containing 100mL dehydrated alcohol, after magnetic agitation half an hour,
Adding 300mL 2M aqueous hydrochloric acid solution, magnetic agitation 12 hours, rear sucking filtration, wash, methanol is washed, end temperature 80 DEG C
It is dried 12 hours, obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide powder；
The preparation of composite photo-catalyst matrix platinum/class graphite type carbon nitride:
Weigh tripolycyanamide 5g, insert in porcelain crucible after grinding, spread even, put into temperature 600 DEG C calcining 4 in Muffle furnace little
Time, cool down afterwards, grind and obtain class graphite type carbon nitride powder；
25mg class graphite type carbon nitride powder is joined the reactor filling the aqueous solution that 100mL concentration is 10% methanol
In, ultrasonic disperse 10 minutes, add the chloroplatinic acid aqueous solution of 3.33mL 100mg/L, limit magnetic agitation snare drum bubble 10
Minute nitrogen, rear uses 500 watts of high voltage mercury lamp radiations 1 hour, sucking filtration, and temperature 100 DEG C is vacuum dried 6 hours,
To platinum/class graphite type carbon nitride powder；
The preparation of composite photo-catalyst N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride:
The platinum prepared by 25mg/class graphite type carbon nitride powder joins containing N, N '-dimethyl amido-p-benzyl-two
Imido concentration is in 25mg/L chloroform soln, platinum/class graphite type carbon nitride and N, N '-dimethyl amido-p-
The weight ratio of benzyl-imidodicarbonic diamide is 400: 1, and ultrasonic disperse is after 5 minutes, under dark condition, and 20 DEG C of water of constant temperature
In bath, magnetic agitation 8 hours, obtain mixed solution system；
Being slowly injected into methanol in the mixed solution system that will obtain, the addition of methanol is 5 times of volumes of chloroform, continues magnetic
Power stirs 12 hours, sucking filtration after standing 30 minutes, then washs 3 times with 10mL methanol, 100 DEG C of forced air dryings of temperature
Case is dried 6 hours, i.e. obtains N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride powder
End sample.
Embodiment 5 (comparison)
Platinum/class graphite type carbon nitride photocatalysis hydrogen production purposes:
Platinum/class graphite type carbon nitride powder prepared by weighing 25mg joins and fills 100mL concentration is 10% triethanolamine water
In the light-catalyzed reaction still of solution, under 25 DEG C of water-bath magnetic agitation of constant temperature, to configure the 400 of ＞ 420 nanometer edge filter
Watt xenon lamp is light source, carries out the photocatalysis hydrogen production experiment under visible ray, and the gas generated and amount use gas chromatogram to carry out reality
Time on-line checking.
Embodiment 6
N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride photocatalysis hydrogen production purposes:
Weigh any one composite photo-catalyst N, N '-two obtained by the method for the invention of 25mg embodiment 1-4
Methylamino-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride powder, joining and filling 100mL concentration is 10%
In the light-catalyzed reaction still of triethanolamine aqueous solution, under 25 DEG C of water-bath magnetic agitation of constant temperature, to configure the cut-off of ＞ 420 nanometer
400 watts of xenon lamps of optical filter are light source, carry out the photocatalysis hydrogen production experiment under visible ray, and the gas generated and amount use gas
Phase chromatograph carries out real-time online detection.
Embodiment 7
The cyclical stability test of composite photo-catalyst hydrogen manufacturing performance:
Solution system sucking filtration after embodiment 5 (comparison) and embodiment 6 are carried out 24 hours, composite photo catalyst powder
Rejoin after drying and fill in the light-catalyzed reaction still that 100mL concentration is 10% triethanolamine aqueous solution, constant temperature 25 DEG C
Under water-bath magnetic agitation, with configure ＞ 420 nanometer edge filter 400 watts of xenon lamps as light source, carry out the light under visible ray
Catalyzing manufacturing of hydrogen is tested, and the gas generated and amount use gas chromatogram to carry out real-time online detection, and result shows 72 hours in,
The hydrogen manufacturing performance of composite photo-catalyst of the present invention is dropped by less than 15%.(Fig. 5)
Claims (5)
1. the method that composite photo-catalyst prepared by a photosensitizer, it is characterised in that the photosensitizer in the method is N, N '-dimethyl amido-p-benzyl-imidodicarbonic diamide, concrete operations follow these steps to carry out:
A, platinum/class graphite type carbon nitride powder is joined containing N, N '-dimethyl amido-pIn the chloroform soln of-benzyl-imidodicarbonic diamide, ultrasonic disperse is after 5 minutes, under dark condition, and magnetic agitation 6-12 hour in 20 DEG C of water-baths of constant temperature, obtain mixed solution system；
Being slowly injected into methanol in b, mixed solution system step a obtained, continue stirring 6-12 hour, sucking filtration after standing 30 minutes, again with methanol is washed, in 100 DEG C of air dry ovens of temperature dry 6 hours, i.e. obtains composite photo-catalyst N, and N '-dimethyl amido-p-benzyl-imidodicarbonic diamide/platinum/class graphite type carbon nitride.
The method of composite photo-catalyst prepared by photosensitizer the most according to claim 1, it is characterised in that platinum/class graphite type carbon nitride and N in step a, and N '-dimethyl amido-pThe weight ratio of-benzyl-imidodicarbonic diamide is 200-400: 1.
The method of composite photo-catalyst prepared by photosensitizer the most according to claim 1, it is characterised in that in step a, chloroform soln concentration is 10-25 mg/L.
The method of composite photo-catalyst prepared by photosensitizer the most according to claim 1, it is characterised in that in step b, the addition of methanol is 4-5 times of volume of chloroform.
5. the composite catalyst of the method for claim 1 acquisition purposes in visible light responsible photocatalytic decomposition water hydrogen making.
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