CN104801318A - Photocatalyst, preparation method thereof, and application of photocatalyst in preparation of hydrogen - Google Patents
Photocatalyst, preparation method thereof, and application of photocatalyst in preparation of hydrogen Download PDFInfo
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Abstract
The invention relates to a photocatalyst, a preparation method thereof, and application of the photocatalyst in preparation of hydrogen, and belongs to the technical field of preparation of hydrogen through photocatalysis. The photocatalyst consists of a carrier SiO2 and a semiconductor component MS, and the constitution form of the photocatalyst is MS(x)@SiO2; the semiconductor component is a metal sulfide, the percentage x of the mass of the semiconductor component in the total mass of the photocatalyst is 1-50%; the semiconductor component is uniformly dispersed on the surface of the carrier or inside holes of the carrier; a metal (s) in the metal sulfide is (are) one or more of cadmium, zinc, copper, indium, silver, nickel and gallium. Through the adoption of the photocatalyst prepared by the preparation method disclosed by the invention, under the condition that only the semiconductor and the inert SiO2 carrier thereof are available, the effect of preparing hydrogen by efficient utilization of sunlight through catalysis can be achieved without the assistance of an auxiliary catalyst like noble metal. The use amount of the semiconductor in the photocatalyst is reduced, so that the cost of the photocatalyst is reduced, and the popularization and application are facilitated.
Description
Technical field
The invention belongs to photocatalysis hydrogen making technical field, be specifically related under one only exists semiconductor and inertia silica supports condition thereof, without the need to by the cocatalysts such as noble metal, preparation method and the application in hydrogen making thereof.
Background technology
Hydrogen Energy a kind ofly has high fuel value, high efficiency and the clean energy, mates and compatible with present most energy resource system, can facilitate, change into electricity and heat efficiently.Hydrogen can also be widely used in chemical process as bulk chemical, can realize CO as utilized hydrogen
2conversion etc., therefore receive industrial quarters and society very big concern.
According to statistics, the reformation that the hydrogen of more than 99% depends on the fossil resources such as coal, oil, natural gas in the world at present obtains (such as: C+2H
2o → 2H
2+ CO
2), along with the increase of hydrogen demand amount and the consumption day by day of fossil resource, utilize the method for fossil resource hydrogen manufacturing not to be the strategy of sustainable development, the consumption of nonrenewable resources will inevitably be aggravated and bring the problem of environmental pollution.Therefore, find technical strategies, develop new, good efficiency, low cost hydrogen producing technology and national energy security and sustainable economic development are had very important significance.
With the renewable material such as water, living beings for raw material, utilizing huge, the eco-friendly advantage of solar energy reserves, is one of desirable route fundamentally solving the energy and problem of environmental pollution through suitable photochemical catalyst hydrogen manufacturing.Since Fujishima and Homda in 1972 is at TiO
2semiconductor has found photocatalytic effect, and achieved since decomposition water obtains photoelectric current, various countries researcher has carried out large quantifier elimination in photocatalysis hydrogen production.The strongest composition that distributes in solar spectrum on the one hand mainly concentrates on the visible region of 400nm ~ 700nm, and the catalyst that exploitation has visible absorption has great importance; On the other hand, the overwhelming majority have photocatalytic activity single semiconductor light-catalyst itself produce hydrogen activity and stability all undesirable.Research finds that semiconductor itself and some noble metals or the semiconductor with low energy gap are combined (i.e. co-catalyst) can improve product hydrogen activity, carry on the composite catalyst of platinum as national inventing patent (ZL200610041835.7) at CdS/Ti-MCM-41, although can hydrogen generation efficiency be improved, the noble metal such as platinum, gold because it is rare, high in cost of production problem will greatly be limited in industry amplify in application; At present about some non-noble metal co-catalysts, as low-gap semiconductor molybdenum sulfide, tungsten sulfide etc. in patent ZL200610011445.5, although although can reduce costs relative to noble metal, but this type of co-catalyst synthesis step is loaded down with trivial details, generally need the process (as patent ZL201110033996.2, ZL201110144999.3 etc.) experiencing the relative harsh conditions such as high-temperature roasting, and this type of co-catalyst has relative specificity, explore the effective co-catalyst to a large amount of photochemical catalyst found at present, also need one section of long time.
In addition, the efficiency existed for semiconductor catalyst is low, the problem of poor stability, if start with to the modification of bulk semiconductor, the cost of noble metal great number can not only be avoided, and by more rational building-up process, reduce complicated processes to the loss of catalyst, realize real estate hydrogen process efficient under visible ray, undoubtedly promotion solar energy hydrogen production by water decomposition is had great importance.
Summary of the invention
Aquatic products hydrogen Problems existing is decomposed for existing photocatalytic semiconductor, the invention provides under one only exists semiconductor and inertia silica supports condition thereof, without the need to by cocatalysts such as noble metals, efficiency utilization sunlight catalytic hydrogen making can be realized, can effectively solve the problem.
Technical scheme provided by the invention is as follows:
A kind of catalyst for photocatalysis Decomposition aquatic products hydrogen provided by the invention, it is characterized in that, this catalyst is by carrier S iO
2form with semiconductor component MS, its composition form is MS (x) SiO
2; Semiconductor group is divided into metal sulfide, and it accounts for x=1% ~ 50% of catalyst gross mass; Semiconductor component is dispersed in carrier surface uniformly or carrier duct is inner.
Preferably, the metal in described metal sulfide is one or more in cadmium, zinc, copper, indium, silver, nickel, gallium.
Preferably, 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 first through infusion process or sol-gal process prepares metal oxide supported in silica composite, and it consists of MO (x) SiO
2; And then through ion-exchange or gas phase synthesis method, preparing photochemical catalyst of the present invention, it consists of MS (x) SiO
2, wherein:
MO is one or more in the oxide of cadmium, zinc, copper, indium, silver, nickel, gallium;
MS is one or more in the sulfide of cadmium, zinc, copper, indium, silver, nickel, gallium;
X is the mass percent of MO in photochemical catalyst, 1≤x≤50.
It is as follows that described infusion process prepares the metal oxide supported step in silica composite:
(1) be dissolved in the water by soluble metal inorganic salts, obtain the aqueous solution of slaine, concentration is 0.05 ~ 1.0g/mL;
(2) non-solubility support precursor joined in the solution of step (1), obtain suspension, wherein, non-solubility support precursor is 0.03 ~ 0.5:1 with the used in molar ratio ratio of soluble metal inorganic salts;
(3) suspension that step (2) obtains at room temperature is stirred 3 ~ 5 hours, the water-bath evaporating water being then placed in 70 ~ 90 degrees Celsius obtains blocks of solid;
(4) blocks of solid that step (3) obtains is placed in air atmosphere, 550 ~ 650 degrees Celsius of lower roastings 3 ~ 5 hours, is cooled to grinds powder after room temperature, obtains metal oxide supported in silica composite MO (x) SiO
2.
Preferably, described soluble metal inorganic salts are one or more in cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, gallium nitrate;
Described non-solubility carrier is for being Kiselgel A (molecular formula xSiO
2yH
2o, average pore size 2.0 ~ 3.0nm, specific surface 650 ~ 800m
2/ g, pore volume 0.35 ~ 0.4mL/g, specific heat 0.92KJ/ (kgK), thermal conductivity factor 0.63KJ/ (mhK)), silochrom (macro porous silica gel, molecular formula xSiO
2yH
2o, pore volume is 0.60 ~ 0.85mL/g, and average pore size is 4.5 ~ 7.0nm, and specific surface is 450 ~ 650m
2/ g), mesoporous silicon oxide (molecular formula SiO
2, average pore size 3 ~ 5nm, pore volume is 0.5 ~ 1.0mL/g, and specific surface is 600 ~ 900m
2/ g) in one or more.
It is as follows that described sol-gal process prepares the metal oxide supported step in 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, and the concentration of soluble metal inorganic salts is 5 ~ 30g/L;
(2) joined by soluble carrier presoma in step (1) solution, the volume ratio of soluble carrier presoma and step (1) solution is 2:1 ~ 4:1;
(3) regulate pH value of solution to acid, the water-bath evaporating water being then placed in 70 ~ 90 degrees Celsius obtains blocks of solid;
(4) solid step (3) obtained, air atmosphere, 550 ~ 650 degrees Celsius of lower roastings 3 ~ 5 hours, is cooled to grinds powder after room temperature, obtains metal oxide supported in compound MO (x) SiO of silica
2;
Preferably, described organic molecule is citric acid, sucrose, glucose or tartaric acid;
Described soluble metal inorganic salts are one or more in cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, gallium nitrate;
Described soluble carrier presoma is ethyl orthosilicate;
The post of described adjustment pH is solution water desetting is g., jelly-like.
The step that described ion-exchange prepares photochemical catalyst is as follows:
(1) metal oxide supported in silica composite (MO (x) SiO by what prepare through infusion process or sol-gal process
2) be distributed to containing S
2-6 ~ 12 hours are processed in the solution of ion, wherein, compound and S
2-the mol ratio of ion is 0.8 ~ 1.2:1;
(2) by step (1) product distilled water or ethanol washing suction filtration, then under 80 ~ 100 degrees Celsius, washed product is dried, namely obtain photochemical catalyst (MS (x) SiO that metal sulfide is carried on silica
2).
Preferably, described containing S
2-the solution of ion is vulcanized sodium, potassium sulfide or ammonium sulfide solution.
The step that described gas phase synthesis method prepares photochemical catalyst is as follows:
Metal oxide supported in silica composite (MO (x) SiO by what prepare through infusion process or sol-gal process
2) in hydrogen sulfide atmosphere, process 0.5 ~ 2 hour under 300 ~ 500 degrees Celsius, namely obtain photochemical catalyst (MS (x) SiO that metal sulfide is carried on silica
2).
Advantage of the present invention is as follows:
The invention provides and a kind ofly can decompose the Catalysts and its preparation method of aquatic products hydrogen by high efficiency photocatalysis under full solar spectrum, under the condition not using any noble metal or base metal co-catalyst, and when keeping lower semiconductor quality percentage, hydrogen generation efficiency efficiently can be reached, not only reduce catalyst cost, save resource, and avoided harsh synthesis condition, catalyst has been promoted the use of and is significant.
Accompanying drawing explanation
Fig. 1: MS of the present invention (15) SiO
2powder electronic diffraction (XRD) collection of illustrative plates;
Fig. 2: MS of the present invention (15) SiO
2ultravioletvisible absorption (UV-vis) spectrogram;
Fig. 3: CdS of the present invention (15) SiO
2n
2adsorption-desorption curve and graph of pore diameter distribution;
Fig. 4: CdS of the present invention (15) SiO
2high resolution transmission electron microscopy (TEM) photo.
Fig. 5: ZnCdS of the present invention (15) SiO
2high resolution transmission electron microscopy (TEM) photo.
As shown in Figure 1, the different metal sulfide compound be carried on silica presents the characteristic signal peak (Fig. 1 b) of respective metal sulfide, and diffraction maximum is wider generally, illustrates that metal sulfide uniform particle is dispersed on carrier; Wherein with sample CdS (15) SiO
2for representative have obvious CdS (111), (220), (Fig. 1 a), is SiO at the broad peaks of about 23 degree to (311) diffraction maximum
2overlapping to form of unformed peak and CdS (111) diffraction maximum.
As shown in Figure 2, the compound that different metal sulfide is carried on silica all has respective absorption band edge in 300 ~ 600nm wave-length coverage, also the difference (Fig. 2 b) of different sample to photoresponse is shown, wherein with sample CdS (15) SiO
2there is strong absorption for representative at 550nm place, belong to that visible light-responded (Fig. 2 a).
As shown in Figure 3, sample CdS (15) SiO
2n
2absorption-desorption curve can be observed a closed hysteresis loop, and according to IUPAC standard, this type of thermoisopleth belongs to IV type, is the characteristic feature of mesoporous material.
As shown in Figure 4, sample CdS (15) SiO
2what middle CdS particle was relatively uniform is distributed in SiO
2on carrier, (a), lattice fringe spacing 0.337nm also meets (111) crystal face (Fig. 4 b) of CdS to Fig. 4, and the mean size of CdS particle is 8nm.
As shown in Figure 5, sample ZnCdS (15) SiO
2also present and CdS (15) SiO
2the feature that sample is similar, metal sulfide uniform particle is dispersed on carrier (Fig. 5 a), and the lattice fringe of confront crosswise (Fig. 5 b) and different lattice fringe spacing (Fig. 5 c) also prove that ZnS and CdS particle has successfully been incorporated on carrier.
Detailed description of the invention
Embodiment 1: infusion process is prepared metal oxide supported in silica composite, i.e. MO (x) SiO
2
Taking 0.13g cadmium nitrate is dissolved in 20mL water, wiring solution-forming; 0.5g non-solubility carrier silica gel is dispersed in above-mentioned solution, is made into suspension; Suspension obtained above is at room temperature stirred 4 hours, is then placed in that the water-bath 10 of 80 degrees Celsius is little obtains blocks of solid up to evaporating water; The solid obtained is placed in the lower 600 degrees Celsius of lower roastings of air atmosphere 3 hours, grinds powder after cooling, obtains metal oxide supported in silica composite, i.e. MO (x) SiO
2, product quality is 4.89g.
Embodiment 2-10: infusion process is prepared metal oxide supported in silica composite, i.e. MO (x) SiO
2
Adopt the preparation technology identical with embodiment 1, only change the kind of metal inorganic salt, consumption, non-solubility kind of carrier, stirred at ambient temperature time, bath temperature, water bath time, sintering temperature and time, infusion process is adopted to prepare metal oxide supported in silica composite, i.e. MO (x) SiO
2, each operation parameter is in table 1 and table 2.
The reaction condition of table 1: embodiment 2-5 and result
The reaction condition of table 2: embodiment 6-10 and result
Embodiment 11: sol-gal process is prepared metal oxide supported in silica composite
(1) the metal inorganic salt cadmium nitrate of 4.3g organic molecule citric acid and 0.15g solubility is dissolved in 7.5mL water, obtains solution;
(2) soluble carrier presoma ethyl orthosilicate is quantitatively joined in the solution that (1) obtain;
(3) regulate pH value of solution to be g., jelly-like to solution water desetting, be placed in that the water-bath 10 of 80 degrees Celsius is little obtains blocks of solid up to evaporating water;
(4) solid that (3) obtain is placed in the lower 600 degrees Celsius of lower roastings of air atmosphere 3 hours, grinds powder after cooling, obtains cadmium oxide and is carried on silica, be i.e. CdO (1) SiO
2;
Adopt the preparation technology identical with embodiment 11, only change the kind of metal inorganic salt, consumption, the kind of organic molecule, bath temperature, water bath time, sintering temperature and time, sol-gal process is adopted to prepare metal oxide supported in silica composite, i.e. MO (x) SiO
2, each operation parameter is in table 3 and table 4.
Embodiment 12-19: sol-gal process is prepared metal oxide supported in silica composite
The reaction condition of table 3: embodiment 12-15 and result
The reaction condition of table 4: embodiment 16-19 and result
Embodiment 20-27: ion-exchange prepares the photochemical catalyst of final finished catalyst, and be MS (x) SiO
2
(1) 0.5g is obtained metal oxide supported be distributed in silica composite a certain amount of containing S
2-(0.05mol/L) 6 ~ 12 hours are processed in solution;
(2) with certain solvent wash suction filtration, then in the baking oven of 80 ~ 100 degrees Celsius 12 ~ 24 hours, catalyst photochemical catalyst finished product MS (x) SiO is namely obtained
2.
In above-mentioned preparation technology, only concrete first fixed following relevant parameter is prepared, each reaction condition reference table 5, preparation-obtained catalyst.
The reaction condition of table 5: embodiment 20-23 and result
The reaction condition of table 6: embodiment 24-27 and result
Embodiment 28-37: ion-exchange prepares final finished catalyst, i.e. MS (x) SiO
2
0.5g is obtained metal oxide supported in silica composite at H
2in the atmosphere of S, 300 ~ 500 degrees Celsius of lower reaction treatment 0.5 ~ 2 hour, namely obtain catalyst photochemical catalyst finished product MS (x) SiO
2.
In above-mentioned preparation technology, only concrete first fixed following relevant parameter is prepared, each reaction condition reference table 5, preparation-obtained catalyst.
The reaction condition of table 7: embodiment 28-32 and result
The reaction condition of table 8: embodiment 33-37 and result
Embodiment 38
For catalyst prepared by embodiment 25-37, adopt the Xe lamp simulated solar irradiation of the 300W of reaction CEL-HXF, carry out in the microreactor that inert gas argon gas stream is dynamic, reaction condition is: catalyst amount 0.1g, reacts at 100mL Na
2s (concentration 0.35mol/L) and Na
2sO
3carry out in the sacrifice reagent of (concentration 0.25mol/L), reaction temperature is 15 DEG C, and the reaction time is 3 hours, H after reaction
2amount by gas-chromatography on-line analysis, the generation speed of hydrogen is listed in table 9:
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 |
Can find out that catalyst prepared by the present invention, only having under semiconductor and inertia silica supports condition thereof, without the need to by cocatalysts such as noble metals, can realize the effect of efficiency utilization sunlight catalytic hydrogen making by testing above.Wherein, be representative with cadmium sulfide in the present invention, carefully analyze its content (1% ~ 50%) to the impact of producing hydrogen activity, find the increase along with CdS content, hydrogen output presents the trend first increasing and reduce afterwards, and in the research range of CdS mass fraction 1% ~ 50% in scope, hydrogen output has obvious advantage relative to the hydrogen output of the single CdS now reported.
In addition, the different sulfide combination loads that the present invention lists are on silica, wherein and do not mean that sulfide combination be only limitted to described in embodiment, extensively can extend to the metal sulfide semiconductor that other respond photocatalysis, and the content of catalytic effect optimum is determined according to different sulfide combination.
Claims (9)
1. a photochemical catalyst, is characterized in that: this catalyst is by carrier S iO
2form with semiconductor component MS, its composition form is MS (x) SiO
2; Semiconductor group is divided into metal sulfide, and it accounts for x=1% ~ 50% of catalyst gross mass; Semiconductor component is dispersed in carrier surface uniformly or carrier duct is inner; Metal in metal sulfide is one or more in cadmium, zinc, copper, indium, silver, nickel, gallium.
2. the preparation method of photochemical catalyst according to claim 1, its step is as follows:
(1) by metal oxide supported compound MO (x) SiO in silica
2be distributed to containing S
2-6 ~ 12 hours are processed in the solution of ion, wherein, compound and S
2-the mol ratio of ion is 0.8 ~ 1.2:1;
(2) by step (1) product distilled water or ethanol washing suction filtration, then under 80 ~ 100 degrees Celsius, washed product is dried, namely obtain photochemical catalyst MS (x) SiO that metal sulfide is carried on silica
2.
3. the preparation method of photochemical catalyst according to claim 1, is characterized in that: by metal oxide supported in silica composite MO (x) SiO
2in hydrogen sulfide atmosphere, process 0.5 ~ 2 hour under 300 ~ 500 degrees Celsius, namely obtain photochemical catalyst MS (x) SiO that metal sulfide is carried on silica
2.
4. the preparation method of photochemical catalyst as claimed in claim 2 or claim 3, is characterized in that: adopt infusion process to prepare metal oxide supported in the compound of silica, its step is as follows,
(1) be dissolved in the water by soluble metal inorganic salts, obtain the aqueous solution of slaine, concentration is 0.05 ~ 1.0g/mL;
(2) non-solubility support precursor joined in the solution of step (1), obtain suspension, wherein, non-solubility support precursor is 0.03 ~ 0.5:1 with the used in molar ratio ratio of soluble metal inorganic salts;
(3) suspension that step (2) obtains at room temperature is stirred 3 ~ 5 hours, the water-bath evaporating water being then placed in 70 ~ 90 degrees Celsius obtains blocks of solid;
(4) blocks of solid that step (3) obtains is placed in air atmosphere, 550 ~ 650 degrees Celsius of lower roastings 3 ~ 5 hours, is cooled to grinds powder after room temperature, obtains metal oxide supported in silica composite MO (x) SiO
2.
5. the preparation method of photochemical catalyst as claimed in claim 4, is characterized in that: soluble metal inorganic salts are one or more in cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, gallium nitrate; Non-solubility carrier is Kiselgel A, macro porous silica gel or mesoporous silicon oxide.
6. the preparation method of photochemical catalyst as claimed in claim 2 or claim 3, is characterized in that: adopt sol-gal process to prepare metal oxide supported in the compound of silica, its step is as follows,
(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, and the concentration of soluble metal inorganic salts is 5 ~ 30g/L;
(2) joined by soluble carrier presoma in step (1) solution, the volume ratio of soluble carrier presoma and step (1) solution is 2:1 ~ 4:1;
(3) regulate pH value of solution to acid, the water-bath evaporating water being then placed in 70 ~ 90 degrees Celsius obtains blocks of solid;
(4) solid step (3) obtained, air atmosphere, 550 ~ 650 degrees Celsius of lower roastings 3 ~ 5 hours, is cooled to grinds powder after room temperature, obtains metal oxide supported in compound MO (x) SiO of silica
2.
7. the preparation method of photochemical catalyst as claimed in claim 6, is characterized in that: organic molecule is citric acid, sucrose, glucose or tartaric acid; Soluble metal inorganic salts are one or more in cadmium nitrate, zinc nitrate, copper nitrate, indium nitrate, silver nitrate, nickel nitrate, gallium nitrate; Soluble carrier presoma is ethyl orthosilicate.
8. the preparation method of photochemical catalyst as claimed in claim 6, is characterized in that: the post of described adjustment pH is solution water desetting is g., jelly-like.
9. the application of photochemical catalyst according to claim 1 in hydrogen making.
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| CN108745382A (en) * | 2018-06-27 | 2018-11-06 | 福州大学 | A kind of preparation method and applications of the CdS visible light catalysts of NiCd double non-noble metals modification |
| CN108745382B (en) * | 2018-06-27 | 2021-03-02 | 福州大学 | Preparation method and application of NiCd double non-noble metal modified CdS visible-light-driven photocatalyst |
| CN109174127A (en) * | 2018-09-18 | 2019-01-11 | 张玉英 | A kind of photocatalytic water prepares the composite photo-catalyst and preparation method of fuel cell hydrogen |
| CN110227492A (en) * | 2019-04-29 | 2019-09-13 | 中国科学院山西煤炭化学研究所 | A kind of Nano semiconductor photochemical catalyst and preparation method thereof |
| CN112892557A (en) * | 2021-02-04 | 2021-06-04 | 常州大学 | SiO (silicon dioxide)2@CdS@SiO2Preparation method and application of core-shell photocatalyst |
| CN112892557B (en) * | 2021-02-04 | 2023-05-23 | 常州大学 | SiO (silicon dioxide) 2 @CdS@SiO 2 Preparation method and application of core-shell photocatalyst |
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