CN104801318B - A kind of photochemical catalyst, preparation method and its application in hydrogen making - Google Patents
A kind of photochemical catalyst, preparation method and its application in hydrogen making Download PDFInfo
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Abstract
A kind of photochemical catalyst, preparation method and its application in hydrogen making, belong to photocatalysis hydrogen making technical field.The catalyst is by carrier S iO2With semiconductor component MS compositions, its composition form is MS (x) SiO2；Semiconductor group is divided into metal sulfide, and it accounts for x=1%~50% of catalyst gross mass；Semiconductor component is uniformly dispersed in inside carrier surface or carrier duct；Metal in metal sulfide is the one or more in cadmium, zinc, copper, indium, silver, nickel, gallium.The catalyst prepared using the present invention, under the conditions of only semiconductor and its inertia silica supports, without cocatalysts such as noble metals, you can realize the effect efficiently using sunlight catalytic hydrogen making.The consumption of semiconductor is reduced in the present invention in catalyst, so as to reduce catalyst cost, is easily promoted the use of.
Description
Technical field
The invention belongs to photocatalysis hydrogen making technical field, and in particular to one kind only exists semiconductor and its inertia dioxy
Under the conditions of SiClx carrier, without the cocatalysts such as noble metal, preparation method and its application in hydrogen making.
Background technology
Hydrogen Energy is a kind of energy with high fuel value, high efficiency and cleaning, is matched with the energy resource system of currently the majority
And compatibility, can conveniently and efficiently it change into electrically and thermally.Hydrogen is also used as bulk chemical and is widely used in chemical process, such as
CO can be realized using hydrogen2Conversion etc., therefore receive the very big concern of industrial quarters and society.
According to statistics, more than 99% hydrogen depends on reforming for the fossil resources such as coal, oil, natural gas in the world at present
To (for example：C+2H2O→2H2+CO2), with the increase and the increasingly consumption of fossil resource of hydrogen demand amount, utilize fossil resource
The method of hydrogen manufacturing is not the strategy of sustainable development, will necessarily aggravate consuming and bringing asking for environmental pollution for nonrenewable resources
Topic.Therefore, find technical strategies, development it is new, good efficiency, the hydrogen producing technology of low cost be for national energy security and warp
Ji sustainable development has very important significance.
Using the renewable material such as water, biomass as raw material, huge, the environment-friendly advantage of sun energy storage capacity, ECDC are utilized
Suitable photochemical catalyst hydrogen manufacturing is fundamentally to solve one of desirable route of the energy and problem of environmental pollution.Since 1972
Fujishima and Homda are in TiO2It is found that photocatalytic effect on semiconductor, and has realized since decomposition water obtains photoelectric current,
Various countries researcher has carried out substantial amounts of research in terms of photocatalysis hydrogen production.Most strong composition is distributed in one side solar spectrum main
400nm~700nm visible region is concentrated on, catalyst of the exploitation with visible absorption has great importance；The opposing party
Face, single semiconductor light-catalyst of the overwhelming majority with photocatalytic activity produces hydrogen activity in itself and its stability is all undesirable.
Research is found semiconductor in itself with some noble metals or the semiconductor with low energy gap is combined (i.e. co-catalyst) and can improved
Produce hydrogen activity, such as national inventing patent (ZL200610041835.7) CdS/Ti-MCM-41 carry platinum composite catalyst on,
Although hydrogen generation efficiency can be improved, the noble metal such as platinum, gold is put due to that will be limited in industry significantly the problems such as its is rare, cost is high
Big-and-middle application；At present on some non-noble metal co-catalysts, low energy gap is partly led in such as patent ZL200610011445.5
Body molybdenum sulfide, tungsten sulfide etc., although although can reduce cost relative to noble metal, such co-catalyst synthesis step is cumbersome,
Generally require the relatively harsh condition of experience high-temperature roasting etc. processing (such as patent ZL201110033996.2,
ZL201110144999.3 etc.), and such co-catalyst has relative specificity, to explore a large amount of to what is had now been found that
Photochemical catalyst effective co-catalyst, in addition it is also necessary to one section of long time.
In addition, the efficiency for semiconductor catalyst presence is low, the problem of stability is poor, if changing to bulk semiconductor
Property start with, be not only avoided that the cost of noble metal great number, and with more rational building-up process, reduce complicated processes to catalysis
The loss of agent, is realized to efficient real estate hydrogen process under visible ray, undoubtedly important to promoting solar energy hydrogen production by water decomposition to have
Meaning.
The content of the invention
The problem of aquatic products hydrogen is present is decomposed for existing photocatalytic semiconductor, only exists and partly leads the invention provides one kind
Under the conditions of body and its inertia silica supports, without cocatalysts such as noble metals, you can realization efficiently utilizes the sun
Photocatalysis hydrogen making, can effectively solve the above problems.
The technical scheme that the present invention is provided is as follows：
A kind of catalyst for photocatalysis Decomposition aquatic products hydrogen that the present invention is provided, it is characterised in that the catalyst is by carrying
Body SiO2With semiconductor component MS compositions, its composition form is MS (x) SiO2；Semiconductor group is divided into metal sulfide, and it, which is accounted for, urges
X=1%~50% of agent gross mass；Semiconductor component is uniformly dispersed in inside carrier surface or carrier duct.
It is preferred that, the metal in described metal sulfide is the one or more in cadmium, zinc, copper, indium, silver, nickel, gallium.
It is preferred that, the operation wavelength of described catalyst is the full spectrum of sunshine.
The present invention also provides the preparation method of above-mentioned photochemical catalyst, and it is by infusion process or sol-gal process preparation first
Obtain metal oxide supported in silica composite, consisting of MO (x)@SiO2；Then again through ion-exchange or gas
Phase synthesi, prepares photochemical catalyst of the present invention, consisting of MS (x)@SiO2, wherein：
MO is the one or more in the oxide of cadmium, zinc, copper, indium, silver, nickel, gallium；
MS is the one or more in the sulfide of cadmium, zinc, copper, indium, silver, nickel, gallium；
X is mass percents of the MO in photochemical catalyst, 1≤x≤50.
The infusion process prepares metal oxide supported as follows the step of silica composite：
(1) soluble metal inorganic salts are dissolved in the water, obtain the aqueous solution of metal salt, concentration is 0.05~1.0g/
mL；
(2) non-solubility support precursor is added in the solution of step (1), obtains suspension, wherein, non-solubility
The used in molar ratio ratio of support precursor and soluble metal inorganic salts is 0.03~0.5：1；
(3) suspension for obtaining step (2) is stirred at room temperature 3~5 hours, is subsequently placed in 70~90 degrees Celsius of water
Evaporating water obtains blocks of solid in bath；
(4) blocks of solid for obtaining step (3) is placed in air atmosphere, is calcined 3~5 hours under 550~650 degrees Celsius,
Shape of claying into power is cooled to after room temperature, obtains metal oxide supported in silica composite MO (x)@SiO2。
It is preferred that, described soluble metal inorganic salts are cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nitre
One or more in sour nickel, gallium nitrate；
Described non-solubility carrier is Kiselgel A (molecular formula xSiO2·yH2O, 2.0~3.0nm of average pore size, than
650~800m of surface2/ g, 0.35~0.4mL/g of pore volume, specific heat 0.92KJ/ (kgK), thermal conductivity factor 0.63KJ/ (mh
K)), silochrom (macro porous silica gel, molecular formula xSiO2·yH2O, pore volume be 0.60~0.85mL/g, average pore size be 4.5~
7.0nm, is 450~650m than surface2/ g), mesoporous silicon oxide (molecular formula SiO2, 3~5nm of average pore size, pore volume be 0.5~
1.0mL/g, is 600~900m than surface2/ g) in one or more.
The sol-gal process prepares metal oxide supported as follows the step of silica composite：
(1) organic molecule and soluble metal inorganic salts are dissolved in the water, obtain solution；The concentration of organic molecule is
0.7~1.1g/mL, the concentration of soluble metal inorganic salts is 5~30g/L；
(2) soluble carrier presoma is added in step (1) solution, soluble carrier presoma and step (1) are molten
The volume ratio of liquid is 2：1~4：1；
(3) regulation pH value of solution is subsequently placed in evaporating water in 70~90 degrees Celsius of water-bath and obtains blocks of solid to acidity；
(4) solid for obtaining step (3) is calcined 3~5 hours under air atmosphere, 550~650 degrees Celsius, is cooled to
Clayed into power after room temperature shape, obtain metal oxide supported compound MO (x) the@SiO in silica2；
It is preferred that, described organic molecule is citric acid, sucrose, glucose or tartaric acid；
Described soluble metal inorganic salts are cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, nitre
One or more in sour gallium；
Described soluble carrier presoma is tetraethyl orthosilicate；
Described regulation pH post is that solution water desetting is in g., jelly-like.
The step of ion-exchange prepares photochemical catalyst is as follows：
(1) by by infusion process or sol-gal process prepare it is metal oxide supported in silica composite
(MO(x)@SiO2) be distributed to containing S2-Handled 6~12 hours in the solution of ion, wherein, compound and S2-The mol ratio of ion
For 0.8~1.2：1；
(2) step (1) product is washed into suction filtration with distilled water or ethanol, then produced washing under 80~100 degrees Celsius
Thing is dried, that is, obtains photochemical catalyst (MS (x) SiO that metal sulfide is carried on silica2)。
It is preferred that, described contains S2-The solution of ion is vulcanized sodium, potassium sulfide or ammonium sulfide solution.
The step of gas phase synthesis method prepares photochemical catalyst is as follows：
By by infusion process or sol-gal process prepare it is metal oxide supported in silica composite (MO
(x)@SiO2) handled 0.5~2 hour under hydrogen sulfide atmosphere, 300~500 degrees Celsius, that is, obtain metal sulfide and be carried on two
Photochemical catalyst (MS (x) the@SiO of silica2)。
The advantage of the present invention is as follows：
The catalyst and its system of aquatic products hydrogen can be decomposed with high efficiency photocatalysis under full solar spectrum the invention provides a kind of
Preparation Method, under conditions of without using any noble metal or base metal co-catalyst, and keeps relatively low semiconductor quality
In the case of percentage, efficiently hydrogen generation efficiency can be reached, catalyst cost is not only reduced, resource has been saved, and keep away
The synthesis condition of harshness is exempted from, catalyst is promoted the use of and is significant.
Brief description of the drawings
Fig. 1：MS (15)@SiO of the present invention2Powder electronic diffraction (XRD) collection of illustrative plates；
Fig. 2：MS (15)@SiO of the present invention2Ultravioletvisible absorption (UV-vis) spectrogram；
Fig. 3：CdS (15)@SiO of the present invention2N2Adsorption-desorption curve and graph of pore diameter distribution；
Fig. 4：CdS (15)@SiO of the present invention2High resolution transmission electron microscopy (TEM) photo.
Fig. 5：ZnCdS (15)@SiO of the present invention2High resolution transmission electron microscopy (TEM) photo.
As shown in figure 1, the compound that different metal sulfide is carried on silica shows respective metal sulfide
Characteristic signal peak (Fig. 1 b), generally diffraction maximum is relatively wide, illustrates that metal sulfide uniform particle is dispersed on carrier；Wherein
With sample CdS (15)@SiO2It is left at 23 degree for (111), (220), (311) diffraction maximum (Fig. 1 a) for having obvious CdS of representative
Right broad peak is SiO2Unformed peak and CdS (111) diffraction maximum are overlapped to form.
As shown in Fig. 2 different metal sulfide is carried on compound on silica in 300~600nm wave-length coverages
Inside there is respective absorption band edge, also show difference (Fig. 2 b) of the different samples to photoresponse, wherein with sample CdS (15)
SiO2There is strong absorption at 550nm for representative, belong to visible light-responded (Fig. 2 a).
As shown in figure 3, sample CdS (15)@SiO2N2The hysteresis loop of a closing can be observed in absorption-desorption curve,
According to IUPAC standards, such thermoisopleth belongs to IV types, is the characteristic feature of mesoporous material.
As shown in figure 4, sample CdS (15)@SiO2Middle CdS particles it is relatively uniform be distributed in SiO2It is brilliant on carrier (Fig. 4 a)
Lattice fringe spacing 0.337nm also complies with CdS (111) crystal face (Fig. 4 b), and the mean size of CdS particles is 8nm.
As shown in figure 5, sample ZnCdS (15)@SiO2Also show and CdS (15)@SiO2The characteristics of sample is similar, metal
Sulfide particles are dispersed on carrier (Fig. 5 a), and between the relative lattice fringe (Fig. 5 b) intersected and different lattice fringes
Also demonstrate that ZnS and CdS particles have been successfully introduced on carrier away from (Fig. 5 c).
Embodiment
Embodiment 1：Infusion process prepares metal oxide supported in silica composite, i.e. MO (x)@SiO2
Weigh 0.13g cadmium nitrates to be dissolved in 20mL water, wiring solution-forming；0.5g non-solubility carrier silica gels are dispersed in above-mentioned
In solution, suspension is made into；Suspension obtained above is stirred at room temperature 4 hours, 80 degrees Celsius of water-bath is subsequently placed in
In obtain blocks of solid to evaporating water within 10 hours；Obtained solid is placed in roasting 3 under lower 600 degrees Celsius of air atmosphere small
When, shape of being clayed into power after cooling obtains metal oxide supported in silica composite, i.e. MO (x)@SiO2, product quality
It is 4.89g.
Embodiment 2-10：Infusion process prepares metal oxide supported in silica composite, i.e. MO (x)@SiO2
Using preparation technology same as Example 1, the only species of change metal inorganic salt, consumption, non-solubility carrier
Species, at room temperature mixing time, bath temperature, water bath time, sintering temperature and time, metal oxide is prepared using infusion process
It is carried on silica composite, i.e. MO (x)@SiO2, it is each to see Tables 1 and 2 using parameter.
Table 1：Embodiment 2-5 reaction condition and result
Table 2：Embodiment 6-10 reaction condition and result
Embodiment 11：Sol-gal process prepares metal oxide supported in silica composite
(1) 4.3g organic molecules citric acid and the soluble metal inorganic salt cadmium nitrates of 0.15g are dissolved in 7.5mL water
In, obtain solution；
(2) soluble carrier presoma tetraethyl orthosilicate is quantitatively adding in the solution that (1) is obtained；
(3) regulation pH value of solution to solution water desetting is in g., jelly-like, is placed in 80 degrees Celsius of water-bath 10 hours to being evaporated
Moisture obtains blocks of solid；
(4) solid for obtaining (3) is placed under lower 600 degrees Celsius of air atmosphere and is calcined 3 hours, is clayed into power after cooling
Shape, obtains cadmium oxide and is carried on silica, i.e. CdO (1)@SiO2；
Using species, consumption, the kind of organic molecule with the identical preparation technology of embodiment 11, only change metal inorganic salt
Class, bath temperature, water bath time, sintering temperature and time, prepared using sol-gal process metal oxide supported in titanium dioxide
Silicon compound, i.e. MO (x)@SiO2, it is each to be shown in Table 3 and table 4 using parameter.
Embodiment 12-19：Sol-gal process prepares metal oxide supported in silica composite
Table 3：Embodiment 12-15 reaction condition and result
Table 4：Embodiment 16-19 reaction condition and result
Embodiment 20-27：Ion-exchange prepares the photochemical catalyst of final finished catalyst, and i.e. MS (x)@SiO2
(1) by 0.5g obtain it is metal oxide supported be distributed in silica composite it is a certain amount of containing S2-
Handled 6~12 hours in the solution of (0.05mol/L)；
(2) suction filtration is washed with certain solvent, then 12~24 hours in 80~100 degrees Celsius of baking oven, that is, obtained
Catalyst photochemical catalyst finished product MS (x)@SiO2。
In above-mentioned preparation technology, prepared by only specific first fixed following relevant parameter, each reaction condition reference table 5, institute
The catalyst prepared.
Table 5：Embodiment 20-23 reaction condition and result
Table 6：Embodiment 24-27 reaction condition and result
Embodiment 28-37：Ion-exchange prepares final finished catalyst, i.e. MS (x)@SiO2
By 0.5g obtain it is metal oxide supported in silica composite in H2In S atmosphere, it is 300~500 Celsius
The lower reaction treatment of degree 0.5~2 hour, that is, obtain catalyst photochemical catalyst finished product MS (x) SiO2。
In above-mentioned preparation technology, prepared by only specific first fixed following relevant parameter, each reaction condition reference table 5, institute
The catalyst prepared.
Table 7：Embodiment 28-32 reaction condition and result
Table 8：Embodiment 33-37 reaction condition and result
Embodiment 38
For embodiment 25-37 prepare catalyst, using reaction CEL-HXF 300W Xe lamp simulated solar irradiations,
Carried out in the microreactor of inert gas argon flow of air, reaction condition is：Catalyst amount 0.1g, reacts in 100mL Na2S
(concentration 0.35mol/L) and Na2SO3Carried out in the sacrifice reagent of (concentration 0.25mol/L), reaction temperature is 15 DEG C, reaction time
For 3 hours, H after reaction2Amount by gas-chromatography on-line analysis, the generation speed of hydrogen is listed in Table 9 below：
Table 9：The hydrogen-producing speed of each embodiment product
| Embodiment | Hydrogen-producing speed (μm ol/h/g) | Embodiment | Hydrogen-producing speed (μm ol/h/g) |
| Embodiment 20 | 3030 | Embodiment 29 | 1750 |
| Embodiment 21 | 1040 | Embodiment 30 | 2880 |
| Embodiment 22 | 4440 | Embodiment 31 | 1020 |
| Embodiment 23 | 9350 | Embodiment 32 | 2030 |
| Embodiment 24 | 2160 | Embodiment 33 | 7080 |
| Embodiment 25 | 2700 | Embodiment 34 | 1130 |
| Embodiment 26 | 8370 | Embodiment 35 | 4570 |
| Embodiment 27 | 2800 | Embodiment 36 | 2560 |
| Embodiment 28 | 7370 | Embodiment 37 | 950 |
Experiment can be seen that catalyst prepared by the present invention more than, in only semiconductor and its inertia silica
Under the conditions of carrier, without cocatalysts such as noble metals, you can realize the effect efficiently using sunlight catalytic hydrogen making
Really.Wherein, using cadmium sulfide as representative in the present invention, influence of its content (1%~50%) to production hydrogen activity, hair have been carefully analyzed
Now with the increase of CdS contents, hydrogen output, which is presented, first increases the trend reduced afterwards, and grinding in CdS mass fractions 1%~50%
In the range of in the range of studying carefully, hydrogen output relative to it has been reported that single CdS hydrogen output have obvious advantage.
In addition, the different sulfide combination loads that the present invention is listed are on silica, wherein being not meant to sulfide
Combination is only limitted to described in embodiment, can be widely popularized the metal sulfide semiconductor responded to other to photocatalysis, and is urged
Depending on changing the optimal content of effect according to the combination of different sulfide.
Claims (2)
1. a kind of photochemical catalyst, it is characterised in that：The catalyst is by carrier S iO2With semiconductor component MS compositions, its composition form
For MS (x)@SiO2；Semiconductor group is divided into metal sulfide, and it accounts for x=1%~30% of catalyst gross mass；Semiconductor component
It is uniformly dispersed in inside carrier surface or carrier duct；Metal in metal sulfide is in cadmium, zinc, copper, indium, silver, nickel, gallium
One or more；And the photochemical catalyst is prepared by following steps,
(1) by metal oxide supported in silica composite MO (x)@SiO2It is distributed to containing S2-Handled in the solution of ion
6~12 hours, wherein, MO (x)@SiO2With S2-The mol ratio of ion is 0.8~1.2：1；
(2) step (1) product is washed into suction filtration with distilled water or ethanol, then dried washed product under 80~100 degrees Celsius
It is dry, that is, obtain photochemical catalyst MS (x) SiO2；
Be prepared using sol-gal process it is metal oxide supported in silica composite MO (x)@SiO2, its step is,
(1) organic molecule and soluble metal inorganic salts are dissolved in the water, obtain solution；The concentration of organic molecule be 0.7~
1.1g/mL, the concentration of soluble metal inorganic salts is 5~30g/L；
(2) soluble carrier presoma is added in step (1) solution, soluble carrier presoma and step (1) solution
Volume ratio is 2：1~4：1；
(3) regulation pH value of solution is to acidity, and it is in g., jelly-like to make solution water desetting, is subsequently placed in 70~90 degrees Celsius of water-bath and steams
Solid carbon dioxide gets blocks of solid；
(4) solid for obtaining step (3) is calcined 3~5 hours under air atmosphere, 550~650 degrees Celsius, is cooled to room temperature
After clay into power shape, obtain metal oxide supported in silica composite MO (x)@SiO2；
Wherein, the metal in metal oxide is the one or more in cadmium, zinc, copper, indium, silver, nickel, gallium；Soluble metal without
Machine salt is the one or more in cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, gallium nitrate；Organic molecule
For citric acid, sucrose, glucose or tartaric acid；Soluble carrier presoma is tetraethyl orthosilicate；Containing S2-The solution of ion is sulphur
Change sodium, potassium sulfide or ammonium sulfide solution.
2. application of the photochemical catalyst described in claim 1 in hydrogen making.
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