CN103316714A - Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst - Google Patents
Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst Download PDFInfo
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- CN103316714A CN103316714A CN2013102680787A CN201310268078A CN103316714A CN 103316714 A CN103316714 A CN 103316714A CN 2013102680787 A CN2013102680787 A CN 2013102680787A CN 201310268078 A CN201310268078 A CN 201310268078A CN 103316714 A CN103316714 A CN 103316714A
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Abstract
The invention relates to a catalyst for photo-catalytically decomposing water to produce hydrogen and a preparation method of the catalyst. The catalyst CdS/UiO-66 or CdS/UiO-66(NH2) is formed by compounding UiO-66 or UiO-66(NH2) and CdS in the mass ratio of 100: (1-100). The invention further provides the preparation method of the catalyst. The invention further provides a method for photo-catalytically decomposing water to produce hydrogen by the catalyst. The photo-catalyst formed by compounding the CdS/UiO-66 and the CdS/UiO-66(NH2) in situ have a high hydrogen production rate; compared with that of pure CdS, the hydrogen production rate of the compound photo-catalyst is obviously improved.
Description
Technical field
The present invention relates to a kind of photocatalytic hydrogen production by water decomposition Catalysts and its preparation method, also relate to a kind of method of photocatalytic hydrogen production by water decomposition, belong to the photocatalysis technology field.
Background technology
At present fossil energy is just petered out, and it utilizes in the process produced pollution can bring serious environmental problem again.Go to consider environmental problem from the angle of the energy, adopting the reproducible solar energy photocatalytic decomposition water of cleaning to produce the Hydrogen Energy of being convenient to utilize is the desirable approach that solves energy problem, develops the key point that high performance photocatalytic hydrogen production by water decomposition catalyst has then become to utilize this method.
In the last few years, based semiconductor photochemical catalyst and semiconductor composite prepared hydrogen and have caused widely and to pay close attention to.CdS is that bandwidth is the n type semiconductor of 2.4eV, has visible absorption and photocatalytic hydrogen production by water decomposition performance.But common CdS particle is easily reunited, and cause its specific area to descend, and the particle light induced electron hole after assembling is easier to be compound, causes its photocatalysis performance to reduce.
For thereby the degree of scatter that improves CdS improves its photocatalytic activity, CN102266787A(number of patent application 201010192443.7) technical scheme that provides utilizes Graphene to prepare a kind of high performance photolysis water hydrogen catalyst as co-catalyst and with CdS is compound, owing to having good electron, assembles and transfer function Graphene in this catalyst, promoted effective separation of electron hole, reduce the compound probability of proton, thereby increased photocatalysis efficiency and the light hydrogen production by water decomposition efficient of photochemical catalyst.CN102068996B(number of patent application 201110044496.9) a kind of CdS/MoO has been proposed
3The preparation method of composite photo-catalyst, this catalyst is by Cd (Ac)
22H
2O, (NH
4)
6Mo
7O
244H
2O and thioacetamide join in the acetone or alcohol solution, put into after the sealing that ultrasonic reactor reaction makes again.This composite catalyst is nanometer spherical, and the nanosphere particle diameter is 300-350nm, is to be that the small-particle self assembly of 5-20nm forms by particle diameter, is evenly inlaying the CdS nanocrystal in addition in the nanosphere, and the highest hydrogen-producing speed of this catalyst can reach 5.25mmol/h.CN100351013C(number of patent application 200610041835.7) preparation method that a kind of CdS/Ti-MCM-41 carries the platinum novel composite catalyst has been proposed, this preparation method with softex kw (CTAB) as the template agent, utilize hydro-thermal method to synthesize CTAB/Ti-MCM-41, CTAB/Ti-MCM-41 is obtained Cd with ion-exchange process under the methyl alcohol boiling point
2+The Ti-MCM-41 of exchange vulcanizes Ti-MCM-41 the CdS/Ti-MCM-41 that obtains middle pore matrix again in hydrogen sulfide atmosphere, carry platinum with photoreduction met hod at last and make composite catalyst.The composite catalyst hydrogen-producing speed in light-catalyzed reaction that utilizes this method to make far is better than the cadmium sulfide of traditional co-precipitation method preparation, and hydrogen-producing speed can reach 890 μ molh
-1G
-1
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of photocatalytic hydrogen production by water decomposition catalyst, it is CdS and the MOFs material is compound obtains, this catalyst has higher catalytic efficiency.
The present invention also aims to provide above-mentioned photocatalytic hydrogen production by water decomposition Preparation of catalysts method.
The present invention also aims to provide a kind of method of utilizing above-mentioned catalyst to carry out photocatalytic hydrogen production by water decomposition.
For achieving the above object, the present invention at first provides a kind of photocatalytic hydrogen production by water decomposition catalyst, and it is by MOFs material (UiO-66 or UiO-66 (NH
2)) be composited with CdS, wherein, described CdS and described MOFs material (UiO-66 or UiO-66 (NH
2)) mass ratio be 100:1-100.
Metal organic frame material (Metal-Organnic frameworks, MOFs) be the novel porous material of a class, the method that mainly is transition metal ions or metal cluster and organic ligand by self assembly and crystal engineering forms the mesh skeleton with periodic network structure, has characteristics such as structure is adjustable, porosity is high, even aperture distribution because of it.Above-mentioned catalyst provided by the present invention is to utilize MOFs material (UiO-66 or the UiO-66 (NH with good hydrothermal stability
2)) the novel photocatalysis hydrogen production by water decomposition catalyst for preparing of the compound CdS of original position.This photocatalytic hydrogen production by water decomposition has the photocatalysis hydrogen production efficient higher than pure CdS with catalyst.
The present invention also provides above-mentioned photocatalytic hydrogen production by water decomposition Preparation of catalysts method, and it is to adopt every source (cadmium acetate), sulphur source (dimethyl sulfoxide (DMSO)) to be initial feed with the MOFs material, to make composite catalyst by solvent thermal reaction.This preparation method can may further comprise the steps:
With UiO-66 or the UiO-66 (NH after the 0.001-0.1g activation
2) join in the dimethyl sulfoxide (DMSO) of 10-100mL, at 25-35 ℃ stirred in water bath 30-60 minute, obtain UiO-66 or UiO-66 (NH
2) solution;
Cadmium acetate is joined described UiO-66 or UiO-66 (NH
2) in the solution, continue to stir 3-6 hour, obtain reactant mixture, wherein, the addition of described cadmium acetate accounts for the 0.1%-5% of described reactant mixture gross mass;
Described reactant mixture is transferred in the autoclave, handled 12-15 hour at 150-200 ℃ of constant temperature, naturally cool to room temperature, with ethanol product is washed, again described product is put in the autoclave that ethanol is housed and handled 10-12 hour at 80-100 ℃ of constant temperature, end product is carried out centrifugal treating, obtained described photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66 or CdS/UiO-66 (NH down in dry 10-24 hour at 80-120 ℃ then
2).
In above-mentioned preparation method, preferably, consumption of ethanol is 10-50mL.
In above-mentioned preparation method, preferably, the rotating speed of centrifugal treating changes for per minute 5000-8000.
In above-mentioned preparation method, preferably, the UiO-66 after the activation or UiO-66 (NH
2) prepare by following steps:
With 0.001-1gUiO-66 or UiO-66 (NH
2) be dispersed in the carrene of 10-50ml, carry out the ultrasonic processing of 20-30min under the 60-90Hz, handled 12-24 hour at 50-100 ℃ of constant temperature, carry out centrifugation then, handle at the constant temperature that the 100-150 ℃ of product that separation is obtained carried out 12-24 hour, obtain UiO-66 or UiO-66 (NH after the described activation
2).
UiO-66 of the present invention, UiO-66 (NH
2) can be synthetic according to the method for following two pieces of bibliographical informations:
[1]Cavka?J?H,Jakobsen?S,Olsbye?U,Guillou?N,Lamberti?C,Bordiga?S,Lillerud?K?P.Anew?zirconium?inorganic?building?brick?forming?metal?organic?frameworks?with?exceptional?stability.Journal?of?the?American?Chemical?Society,2008,130(42):13850-13851.
[2]Silva?C?G,Luz?I,Xamena?L,Corma?A,García?H.Water?stable?Zr-benzenedicarboxylate?metal-organic?frameworks?as?photocatalysts?for?hydrogen?generation.Chemistry?A?European?Journal,2010,16(2):11133-11138。
The full text of above-mentioned document is introduced here as a reference.
According to specific embodiments of the present invention, preferably, UiO-66 prepares by following steps:
0.01-0.1g zirconium chloride and 0.01-0.1g terephthalic acid (TPA) are mixed, again this mixture is dissolved in 10-50g N, in N '-dimethyl formamide, at room temperature stirred 30-60 minute, subsequently mixture is transferred to and contained in the teflon-lined autoclave, and in 100-120 ℃ of baking oven isothermal reaction 24-48 hour, naturally cool to room temperature, obtain white product;
Use the aperture as the G1 sand core funnel of 20-30 μ m white product to be filtered, and using N, N '-dimethyl formamide washing white product carries out centrifugation to filtrate then, the product of centrifugation was put in the 50-100 ℃ of baking oven dry 1-2 hour, obtains UiO-66.
According to specific embodiments of the present invention, preferably, UiO-66 (NH
2) prepare by following steps:
0.01-0.1g zirconium chloride and the amino terephthalic acid (TPA) of 0.01-0.1g2-are mixed, again this mixture is dissolved in 10-50gN, in N '-dimethyl formamide, at room temperature stirred 30-60 minute, subsequently mixture is transferred to and contained in the teflon-lined autoclave, and in 100-120 ℃ of baking oven isothermal reaction 24-48 hour, naturally cool to room temperature, obtain white product;
Use the aperture as the G1 sand core funnel of 20-30 μ m white product to be filtered, and using N, N '-dimethyl formamide washing white product carries out centrifugation to filtrate then, the product of centrifugation was put in the 50-100 ℃ of baking oven dry 1-2 hour, obtains described UiO-66 (NH
2).
The present invention also provides a kind of method of photocatalytic hydrogen production by water decomposition, and it may further comprise the steps:
1-10g vulcanized sodium and 1-10g sodium sulfite as sacrificing agent dissolves in 100-200mL distilled water, are added the above-mentioned photocatalytic hydrogen production by water decomposition of 0.01-1g with catalyst CdS/UiO-66 or CdS/UiO-66 (NH
2), under the frequency of 60-90Hz, carry out 20-30 minute ultrasonic processing then, obtain reactant mixture;
Reactant mixture is placed the reaction unit of sealing, and reaction unit is vacuumized, reach a negative atmospheric pressure after, greater than the visible light source of 420nm reactant mixture is shone to produce hydrogen with wavelength again.
In the method for above-mentioned photocatalytic hydrogen production by water decomposition, preferably, the visible light source that adopts is xenon source.
In the method for above-mentioned photocatalytic hydrogen production by water decomposition, preferably, in course of reaction, described reactant mixture is under the continuous stirring.
Technical scheme provided by the present invention has following beneficial effect:
1, CdS/UiO-66 provided by the invention and CdS/UiO-66 (NH
2) two kinds of original position composite photocatalyst hydrogen production by water decomposition have very high hydrogen-producing speed with catalyst, compare with simple CdS, hydrogen-producing speed obviously improves.
2, utilization of the present invention has UiO-66 and the UiO-66 (NH of high-specific surface area and good hydrothermal stability
2) as the carrier of photocatalytic hydrogen production by water decomposition with catalyst, increased the degree of scatter of CdS greatly, reduce its gathering, and then strengthened light decomposition water hydrogen-producing speed.In addition, carrier UiO-66 (NH
2) in because the introducing of amino group, increased visible light-respondedly, photo-generated carrier had capture and transferance, can effectively the electron hole of photoproduction be separated, thereby improve hydrogen-producing speed.
3, photocatalytic hydrogen production by water decomposition provided by the present invention with the Preparation of catalysts method simple and catalytic reaction can at room temperature carry out, be conducive to large-scale promotion.
Description of drawings
Fig. 1 is photochemical catalyzing hydrogen output and the time curve that the photocatalytic hydrogen production by water decomposition of embodiment 1 preparation is used catalyst CdS/UiO-66;
Fig. 2 is the XRD collection of illustrative plates that the photocatalytic hydrogen production by water decomposition of embodiment 1 preparation is used catalyst CdS/UiO-66;
Fig. 3 is the photocatalytic hydrogen production by water decomposition of embodiment 2 preparations catalyst CdS/UiO-66 (NH
2) photochemical catalyzing hydrogen output and time curve;
Fig. 4 is the photocatalytic hydrogen production by water decomposition of embodiment 2 preparations catalyst CdS/UiO-66 (NH
2) the XRD collection of illustrative plates;
Fig. 5 is photochemical catalyzing hydrogen output and the time curve of UiO-66;
Fig. 6 is the XRD collection of illustrative plates of UiO-66;
Fig. 7 is UiO-66 (NH
2) photochemical catalyzing hydrogen output and time curve;
Fig. 8 is UiO-66 (NH
2) the XRD collection of illustrative plates;
Fig. 9 is photochemical catalyzing hydrogen output and the time curve of CdS.
The specific embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, referring now to Figure of description technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as restriction to practical range of the present invention.
The concrete preparation process of the UiO-66 that embodiment adopts is as follows:
Take by weighing zirconium chloride 0.053g and terephthalic acid (TPA) 0.034g, again it is dissolved in 24.9g N, among the N '-dimethyl formamide (DMF), at room temperature stirred 30 minutes, subsequently mixture being transferred to 23mL contains in the teflon-lined autoclave, and isothermal reaction 48 hours in 120 ℃ of baking ovens, naturally cool to room temperature, obtain white product UiO-66;
Excess reactant forms gelatinous precipitate impurity and is blended in the white product, in order to remove impurity, use the aperture to filter above-mentioned white product as the G1 sand core funnel of 20-30 μ m, and use N, N '-dimethyl formamide washing with the filtrate centrifugation, was put into the product that separates in 50 ℃ of baking ovens dry 1 hour for several times again, obtain pure UiO-66 product, its XRD collection of illustrative plates as shown in Figure 6;
Again resulting pure UiO-66 is distributed in the 20ml dichloromethane solution, under the 90HZ after ultrasonic processing half an hour, be transferred in 50 ℃ of baking ovens constant temperature 24 hours, carry out centrifugation then, at last centrifugal resulting product is transferred to that constant temperature namely obtained removing the UiO-66 that guest molecule is activated in 24 hours in 100 ℃ the baking oven.
Change the 0.034g terephthalic acid (TPA) in the above-mentioned preparation process into 0.041g2-amino terephthalic acid (TPA), it is identical that other conditions all keep, and makes the UiO-66 (NH after the activation
2).Prepare pure UiO-66 (NH
2) product the XRD collection of illustrative plates as shown in Figure 8.
Present embodiment provides four kinds of photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66, and it prepares by following steps:
Take by weighing 0.0032g respectively, 0.0064g, 0.0128g, 0.0256g the UiO-66 after the activation, join respectively in the dimethyl sulfoxide solvent of 24mL, and under 25 ℃ of water-baths, stirred 30 minutes, take by weighing four parts of the cadmium acetates of 0.064g more respectively, join respectively in the dimethyl sulphoxide solution of above different UiO-66 content, continue again to stir 3 hours, transferring to 30mL then contains in the teflon-lined autoclave, and constant temperature was handled 12 hours in 180 ℃ of baking ovens, naturally cool to room temperature, with the ethanol washing for several times, again product is respectively put in the autoclave that 24mL ethanol is housed 80 ℃ of constant temperature 12 hours, at last the centrifugal back of product was obtained presoma UiO-66 in dry 12 hours down and the cadmium acetate mass ratio is respectively 5:100 at 100 ℃, 10:100, the photocatalytic hydrogen production by water decomposition of 20:100 and 40:100 catalyst CdS/UiO-66.
Above-mentioned four kinds of photocatalytic hydrogen production by water decomposition characterize as shown in Figure 2 with the XRD of catalyst CdS/UiO-66, as seen from Figure 2: the diffraction maximum that has occurred UiO-66 at low angle, illustrate that above-mentioned photocatalytic hydrogen production by water decomposition is with containing the UiO-66 phase in the catalyst, and the diffraction maximum of CdS has appearred in high angle, illustrate that above-mentioned photocatalytic hydrogen production by water decomposition is with there being CdS in the catalyst.
Present embodiment provides four kinds of photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66 (NH
2), it prepares by following steps:
Change the UiO-66 among the embodiment 1 into UiO-66 (NH
2), other conditions are identical with embodiment 1, make presoma UiO-66 (NH
2) be respectively 5:100,10:100,20:100 and four kinds of ratios of 40:100 with the cadmium acetate mass ratio photocatalytic hydrogen production by water decomposition with catalyst CdS/UiO-66 (NH
2).
These four kinds of photocatalytic hydrogen production by water decomposition with the XRD collection of illustrative plates of catalyst as shown in Figure 4, as seen from Figure 4: UiO-66 (NH occurred at low angle
2) diffraction maximum, illustrate that above-mentioned photocatalytic hydrogen production by water decomposition is with containing UiO-66 (NH in the catalyst
2) phase, and the diffraction maximum of CdS has appearred in high angle, illustrate that above-mentioned photocatalytic hydrogen production by water decomposition is with there being CdS in the catalyst.
Embodiment 3 photochemical catalyzing activity ratings
The Labsolar-II instrument that adopts pool Fei Lai company carries out the evaluation experimental of photochemical catalyzing Mars to catalyst, and this evaluation experimental carries out in such a way:
Taking by weighing the 0.01g catalyst is dissolved in the beaker that contains 100mL distilled water, taking by weighing 4.50g vulcanized sodium and 2.50g sodium sulfite again is dissolved in wherein as sacrificing reagent, then beaker is placed on to stir on the magnetic stirring apparatus and disperses, put into Ultrasound Instrument at last, ultrasonic processing is 20 minutes under the condition of 90Hz;
After ultrasonic the finishing dealing with the reactant in the beaker is transferred in the quartz reactor of photocatalysis apparatus, before the reaction beginning, whole photocatalysis apparatus is vacuumized processing, need reach negative atmospheric pressure;
Adopt the xenon source direct irradiation on quartz reactor, reactant in the reactor is under the stirring always, in 3 hours reaction time, every 30 minutes once sampling, the hydrogen component concentration in the product obtained by the gas-chromatography on-line analysis.
According to above-mentioned steps, four kinds of photocatalytic hydrogen production by water decomposition of embodiment 1 preparation are estimated with catalyst CdS/UiO-66, obtain hydrogen output and time relation curve that they and water react, as shown in Figure 1.The result of Fig. 1 shows: the mass ratio of presoma UiO-66 and cadmium acetate is that the photocatalytic hydrogen production by water decomposition of 10:100 has the highest hydrogen-producing speed with catalyst CdS/UiO-66, and hydrogen-producing speed is 14.2 μ mol/h.
According to the four kind photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66 (NH of above-mentioned steps to embodiment 2 preparations
2) estimate, obtain hydrogen output and the time relation curve of they and water reaction, as shown in Figure 3.The result of Fig. 3 shows: presoma UiO-66 (NH
2) with the mass ratio of cadmium acetate be that the photocatalytic hydrogen production by water decomposition of 10:100 is with catalyst CdS/UiO-66 (NH
2) having the highest hydrogen-producing speed, hydrogen-producing speed is 28.4 μ mol/h.
Comparative Examples 1
According to the photolysis water hydrogen activity that evaluation method and the step of embodiment 3 are investigated simple UiO-66 sample, the result as shown in Figure 5.By the result of Fig. 5 as can be seen: reaction does not have catalytic activity to this sample to photodissociation water.
Comparative Examples 2
Evaluation method and step according to embodiment 3 are investigated simple UiO-66 (NH
2) the photolysis water hydrogen activity of sample, the result is as shown in Figure 7.By the result of Fig. 7 as can be seen: reaction does not have catalytic activity to this sample to photodissociation water.
Comparative Examples 3
Do not add UiO-66 in embodiment 1 process, other reaction conditions remain unchanged, and make simple CdS sample.Investigate the catalytic reaction activity of simple CdS again according to the evaluation method among the embodiment 3 and step, the result as shown in Figure 9.By the result of Fig. 9 as can be seen: the hydrogen-producing speed of simple CdS is 5.4 μ mol/h.
By The above results as can be seen, the photocatalytic hydrogen production by water decomposition of embodiment 1 and embodiment 2 preparations has the photocatalysis higher than simple CdS with catalyst and divides hydrolytic hydrogen production efficient.
Claims (7)
1. photocatalytic hydrogen production by water decomposition catalyst, it is by UiO-66 or UiO-66 (NH
2) be composited with CdS, wherein, described CdS and described UiO-66 or UiO-66 (NH
2) mass ratio be 100:1-100.
2. the described photocatalytic hydrogen production by water decomposition of claim 1 Preparation of catalysts method, it may further comprise the steps:
With UiO-66 or the UiO-66 (NH after the 0.001-0.1g activation
2) join in the dimethyl sulfoxide (DMSO) of 10-100mL, at 25-35 ℃ stirred in water bath 30-60 minute, obtain UiO-66 or UiO-66 (NH
2) solution;
Cadmium acetate is joined described UiO-66 or UiO-66 (NH
2) in the solution, continue to stir 3-6 hour, obtain reactant mixture, wherein, the addition of described cadmium acetate accounts for the 0.1%-5% of described reactant mixture gross mass;
Described reactant mixture is transferred in the autoclave, handled 12-15 hour at 150-200 ℃ of constant temperature, naturally cool to room temperature, with ethanol product is washed, again described product is put in the autoclave that ethanol is housed and handled 10-12 hour at 80-100 ℃ of constant temperature, end product is carried out centrifugal treating, obtained described photocatalytic hydrogen production by water decomposition catalyst CdS/UiO-66 or CdS/UiO-66 (NH down in dry 10-24 hour at 80-120 ℃ then
2).
3. preparation method according to claim 2, wherein, the addition of described ethanol is 10-50mL.
4. preparation method according to claim 1, wherein, the rotating speed of described centrifugal treating is that per minute 5000-8000 changes.
5. the method for a photocatalytic hydrogen production by water decomposition, it may further comprise the steps:
With 1-10g vulcanized sodium and 1-10g sodium sulfite as sacrificing agent dissolves in 100-200mL distilled water, add the described photocatalytic hydrogen production by water decomposition catalyst of 0.01-1g claim 1, under the frequency of 60-90Hz, carry out 20-30 minute ultrasonic processing then, obtain reactant mixture;
Reactant mixture is placed the reaction unit of sealing, and reaction unit is vacuumized, reach a negative atmospheric pressure after, greater than the visible light source of 420nm reactant mixture is shone to produce hydrogen with wavelength again.
6. method according to claim 5, wherein, described visible light source is xenon source.
7. according to claim 5 or 6 described methods, wherein, in course of reaction, described reactant mixture is under the continuous stirring.
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