CN101973519B - Light condensation-light conversion composite reinforced type solar photocatalysis water-decomposition hydrogen-production system - Google Patents
Light condensation-light conversion composite reinforced type solar photocatalysis water-decomposition hydrogen-production system Download PDFInfo
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- CN101973519B CN101973519B CN201010291005A CN201010291005A CN101973519B CN 101973519 B CN101973519 B CN 101973519B CN 201010291005 A CN201010291005 A CN 201010291005A CN 201010291005 A CN201010291005 A CN 201010291005A CN 101973519 B CN101973519 B CN 101973519B
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- 238000007146 photocatalysis Methods 0.000 title claims abstract description 28
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 92
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 90
- 239000001257 hydrogen Substances 0.000 claims description 90
- 238000006555 catalytic reaction Methods 0.000 claims description 60
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- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
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- 150000002500 ions Chemical class 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
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- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 150000008040 ionic compounds Chemical class 0.000 claims description 4
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000005368 silicate glass Substances 0.000 claims description 4
- 235000015281 sodium iodate Nutrition 0.000 claims description 4
- 239000011697 sodium iodate Substances 0.000 claims description 4
- 229940032753 sodium iodate Drugs 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
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- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
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- 235000006666 potassium iodate Nutrition 0.000 claims description 2
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- XUGSDIOYQBRKGF-UHFFFAOYSA-N silicon;hydrochloride Chemical compound [Si].Cl XUGSDIOYQBRKGF-UHFFFAOYSA-N 0.000 description 4
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention provides a light condensation-light conversion composite reinforced type solar photocatalysis water-decomposition hydrogen-production system. The system comprises a solar collection-transmission unit, a light conversion-photocatalysis hydrogen-production reaction unit, a light conversion-photocatalysis oxygen-production reaction unit and a medium cycle control unit. By adopting the dual action of light condensation and light conversion, the response spectral intensity of the photocatalysis is remarkably enhanced, and the medium cycle control unit forcefully ensures the loop exchange and the stable concentration of a reaction medium component. With multiple actions, a photocatalysis material can favorably interact with a reaction medium to generate a high-efficiency and stable photocatalysis hydrogen-production reaction. The system has the advantages of simple structure, strong designability, high photon conversion efficiency, stable performance, and the like, can fully convert and utilize solar energy and suit different sunshine conditions and is easy to popularize and apply on a large scale.
Description
Technical field:
The present invention relates to a kind of optically focused-commentaries on classics photorecombination enhancement type solar energy photocatalytic hydrogen production by water decomposition system, especially a kind of the collection " optically focused, change light and photochemical catalysis " multiple function novel circulation-type solar energy photocatalytic hydrogen production by water decomposition system.
Background technology:
In solving the global energy and ecocrisis; Utilizing the abundant solar energy photocatalytic hydrogen manufacturing conduct of nature is the new forms of energy approach of a Sustainable development; Receive showing great attention to of international community just day by day, the solar energy photocatalytic hydrogen manufacturing material has become one of research focus and emphasis of current technical field of new energies with technology.In several kinds of approach such as solar energy power generating water electrolysis hydrogen production, sun power thermo-chemical decomposition of water and biomass hydrogen preparation, solar energy photocatalytic hydrogen production by water decomposition; It is the most attractive to utilize efficient, stable sunshine photocatalytic material structure new type solar energy directly to decompose pure water hydrogen manufacturing (oxygen) system, and potential economy and social value are huge.
At present, the photocatalysis hydrogen production reaction system mainly comprises photocatalysis Decomposition pure water hydrogen manufacturing system and contains two big types of the reagent hydrogen manufacturing systems of sacrificing.Compare with the latter, have " Z scheme " type photochemical catalysis system of redox characteristic, owing to do not have the consumption of medium, thereby aspect practical application, will have more advantage.Along with the appearance of some novel photocatalysis materials, like modification TiO
2, TaON, Ta
3N
5, BiVO
4Deng.People have made up some new photocatalysis hydrogen production systems, are the reduction photocatalyst with Pt/TaON like Abe etc., with Pt/WO
3For the oxidation photocatalyst, at IO
-3/ I
-Realized the decomposition of water in the solution, quantum yield has reached 0.14%.Pass through ZrO
2, CNs modification and nano-structured, can significantly improve Ta
3N
5Photocatalytic activity, people such as Masashi Tabata are at IO
-3/ I
-The direct decomposing hydrogen-production and system oxygen of water have equally also been realized in the solution.Because light conversion-catalystic converter system performance receives the influence of photocatalyst material spectral response characteristic, photon conversion efficiency and stable numerous factors, up to the present, solar energy photocatalytic hydrogen manufacturing does not reach the practicability performance requriements yet.
Understanding through the domestic and foreign literature data; The modification that photochemical catalysis is effective, mainly to be some at present at ultraviolet, near ultraviolet high-energy photon excite down the photocatalyst material of stable performance responds, photon conversion efficiency is high or unmodified conductor oxidate, oxynitride, nitride material, like C, N, B, doped Ti O
2, TaON, Ta
3N
5, CNTs-Ta
3N
5, BiVO
4Deng, can process photocatalysis thin film through methods such as rf magnetron sputtering, pulsed laser deposition, liquid phase deposition, sol-gels and use.The outer light conversion agent of transparent red through multiphoton process such as two-photon, three-photon with low-energy state infrared photon in the sunshine convert that high-energy state is visible into, near ultraviolet or blue green light.Change the effectively compound of two kinds of differing materials through photochemical catalysis and light, can obtain a kind of new type light conversion-catalytic composite materials that changes light and photo-catalysis function that integrates.Up to the present, this light conversion-catalytic composite materials and with its integrating of being the basis " optically focused, change light and photochemical catalysis " multiple function new type solar energy photocatalytic hydrogen production by water decomposition system also occur.
Summary of the invention:
The purpose of this invention is to provide a kind of efficient, stable optically focused-commentaries on classics photorecombination enhancement type solar energy photocatalytic hydrogen production by water decomposition system.
Technical scheme of the present invention is: a kind of optically focused-commentaries on classics photorecombination enhancement type solar energy photocatalytic hydrogen production by water decomposition system is characterized in that: be made up of solar light collection-transmission unit, light conversion-catalyzing manufacturing of hydrogen reaction member, light conversion-catalysis oxygen making reaction unit and medium circulation control unit; Sunshine is injected into light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit through the collection and the transmission of solar light collection-transmission unit, produces with reaction medium to interact, and the photocatalysis hydrogen production reaction takes place; Wherein light conversion-catalyzing manufacturing of hydrogen reaction member is made up of reactor drum tank body (A), " light conversion-catalysis " hydrogen production reaction array, unitor, gas separation membrane and reaction medium jointly; Solar light collection-transmission unit is made up of Fresnel Lenses, condensing apparatus and solar automatic tracker, optical fibers jointly; Fresnel Lenses is on condensing apparatus; The condensing apparatus bottom connects optical fibers; Light conversion-catalyzing manufacturing of hydrogen reaction member is through the unitor and the fiber-optic output terminal of the solar light collection-transmission unit UNICOM of " light conversion-catalysis " hydrogen production reaction array port, through the hydrogen delivery tube road and the hydrogen-storing device UNICOM on reactor drum tank body (A) top; Light conversion-catalysis oxygen making reaction unit is made up of reactor drum tank body (B), light conversion-catalysis oxygen making reaction array, unitor, reaction medium and gas separation membrane and reaction medium jointly, through the unitor and the fiber-optic output terminal of the solar light collection-transmission unit UNICOM of light conversion-catalysis oxygen making reaction array port; Light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of reaction medium through the medium circulation control unit; Wherein, light conversion-catalyzing manufacturing of hydrogen reaction array is made up of light conversion-catalyzing manufacturing of hydrogen matrix material, and carries out composite design as required; Light conversion-catalysis oxygen making reaction array is made up of light conversion-catalysis system O compoiste material, and carries out composite design as required.
Wherein said light conversion-catalyzing manufacturing of hydrogen matrix material and light conversion-catalysis system O compoiste material be shaped as fibrous, bar-shaped or tubulose.
Described medium circulation control unit is made up of circulating line, recycle pump and concentration of medium modulator jointly, and UNICOM's photocatalysis hydrogen production reaction member and photochemical catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of oxidation-reduction medium; Circulating line links from the top outlet of reactor drum tank body (A) and the bottom inlet of reactor drum tank body (B); Circulating line links from the lower part outlet of reactor drum tank body (A) and the upper entrance of reactor drum tank body (B); Wherein, The concentration of medium modulator is made up of water tank, thrust-augmenting nozzle and flow director, realizes UNICOM through thrust-augmenting nozzle and circulating line.
Described reaction medium is made up of water and oxidation-reduction anion radical jointly; The oxidation-reduction anion radical by the ionic compound of iodine and iodate according to molar ratio 0.5～1: 1, the volumetric molar concentration of oxidation-reduction negatively charged ion in the aqueous solution is 0.1～10%; Wherein, the ionic compound of iodine is at least a kind of of sodium iodide or potassiumiodide, and iodate is at least a kind of of sodium iodate or Potassium Iodate.
Described gas separation membrane 6 is positioned at the circulating line inlet, intercepts light-catalyzed reaction product H
2And O
2Pass through; Gas separation membrane 10 is positioned at the reaction medium top, rises to intercept H
2The effect of O; Gas separation membrane 6 is a perfluoro sulfonic acid membrane, and gas separation membrane 10 is any one in polymeric amide or the polyimide film.
Light conversion-catalyzing manufacturing of hydrogen matrix material of the present invention changes the light sandwich layer outward by transparent red and the photocatalysis hydrogen production rete is formed; Light conversion-catalysis system O compoiste material changes the light sandwich layer outward by transparent red and photochemical catalysis oxygen-producing membrane layer is formed; Wherein, transparent red changes the light sandwich layer outward and is prepared from outer light-converting glass material of transparent red or the outer light-converting glass film composite material of transparent red; The photocatalysis hydrogen production rete is by the composite modified TaON of precious metal, Ta
3N
5, BiVO
4Or modification TiO
2In any one be prepared from; Photochemical catalysis oxygen-producing membrane layer is by the composite modified WO of precious metal
3Be prepared from; Precious metal is at least a kind of among Pt or the Ir.
The outer light-converting glass material of preferred described transparent red is gone up any one in silicate glass, phosphate glass or the oxyfluoride glass of changing the rare earth functional ionic for doping is infrared; The infrared conversion rare earth functional ionic of going up is by sensitized ions Yb
3+With light emitting ionic Tm
3+Or Er
3+In at least a common composition, sensitized ions Yb wherein
3+The doping molar weight is that oxide compound is formed 2～30% of mole total amount in the outer light-converting glass material of transparent red; Yb
3+: (Tm
3+And/or Er
3+) molar ratio be 0.1～5: 10.
The outer light-converting glass film composite material of preferred described transparent red is made up of transparent glass matrix and the outer light conversion film of transparent red jointly; Wherein, the thickness of the outer light conversion film of transparent red is .01～1mm; The transparent glass matrix is any one in silica glass, silicate glass, zeopan glass or the borosilicate glass; The outer light conversion film of transparent red is by silicate or phosphate matrix and nanocrystalline NaYF
4: Yb
3+, (Tm
3+, Er
3+), LiYF
4: Yb
3+, (Tm
3+, Er
3+), YAG:Yb
3+, (Tm
3+, Er
3+) at least a common composition; Nanocrystalline content is 5～30% of used silicate of the outer light conversion film of transparent red or phosphate matrix weight.
Beneficial effect:
1, in new type solar energy photocatalytic hydrogen production by water decomposition system; Sunshine is after overbunching and spectrum conversion dual function; Significantly strengthened photochemical catalysis response spectrum intensity, made photocatalyst material and reaction medium interact, efficient, stable photocatalysis hydrogen production reaction has taken place.
2, new type solar energy photocatalytic hydrogen production by water decomposition system architecture is simple, designability is strong; Have photon conversion efficiency height, steady performance; Fully the conversion using sun power solar irradiation condition different with adaptation is easy to carry out large-scale promotion and application.
Description of drawings:
Fig. 1 structural representation of the present invention;
Wherein: the solar light collection device of 1-solar light collection-transmission unit; The 2-optical fibers; The 3-unitor; 4-light conversion-catalyzing manufacturing of hydrogen reaction array; 5-light conversion-catalysis oxygen making reaction array; The 6-gas separation membrane; The 7-circulating line; The 8-circulating line; The 9-recycle pump; 10-steam separatory membrane; 11-H
2Transport pipe; The 12-flow director; The 13-water tank; The 14-thrust-augmenting nozzle
1 part-structure of Fig. 2 solar light collection-transmission unit: wherein: 15--Nie Er lens, 16--condensing apparatus, 17--solar automatic tracker, 2-optical fibers
Main the looking and left view of the three-in-one optical fiber union of Fig. 3;
Fig. 4 light conversion-catalyzing manufacturing of hydrogen reaction array vertical view.
Embodiment:
Embodiment 1:
Structure of the present invention is as shown in Figure 1: be made up of solar light collection-transmission unit, light conversion-catalyzing manufacturing of hydrogen reaction member, light conversion-catalysis oxygen making reaction unit, medium circulation control unit.
Solar light collection-transmission unit (as shown in Figure 2) is made up of Fresnel Lenses (15), condensing apparatus (16) and solar automatic tracker (17), optical fibers (2) jointly.Fresnel Lenses (15) is on condensing apparatus (16), and condensing apparatus (16) bottom connects optical fibers (2).
Light conversion-catalyzing manufacturing of hydrogen reaction member is by reactor drum tank body (A), the reaction of light conversion-catalyzing manufacturing of hydrogen array (4), reaction solution and gas separation membrane (6; 10) the common composition; Unitor (3 through light conversion-catalyzing manufacturing of hydrogen reaction array (4) port; As shown in Figure 3) with the output terminal UNICOM of solar light collection-transmission unit optical fibers (2), through the hydrogen delivery tube road (11) and the hydrogen-storing device UNICOM on reactor drum tank body (A) top.Light conversion-catalysis oxygen making reaction unit is by reactor drum tank body (B), light conversion-catalysis oxygen making reaction array (5), reaction solution and gas separation membrane (6; 10) the common composition, the output terminal UNICOM of unitor (3) Yu solar light collection-transmission unit optical fibers (2) through light conversion-catalysis oxygen making reaction array (5) port.Light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of reaction medium through the medium circulation control unit.The medium circulation control unit is made up of circulating line (7,8), recycle pump (9), concentration of medium modulator jointly, and UNICOM's photocatalysis hydrogen production reaction member and photochemical catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of oxidation-reduction medium.The concentration of medium modulator is made up of flow director (12), water tank (13) and thrust-augmenting nozzle (14), realizes UNICOM through thrust-augmenting nozzle (14) and circulating line (8).Reaction medium is made up of water, sodium iodate, Soiodin jointly, and the volumetric molar concentration of iodate and iodide ion is 0.5% in the solution.Gas separation membrane (6) is a perfluoro sulfonic acid membrane, and gas separation membrane (10) is a polyimide film.
Light conversion-catalyzing manufacturing of hydrogen reaction array (4) constitutes 3 layers up and down by bar-shaped light conversion-catalyzing manufacturing of hydrogen matrix material, 6 every layer array.Bar-shaped light conversion-catalyzing manufacturing of hydrogen matrix material is by doping 2%Yb
3+And 0.1%Tm
3+The TaON photocatalysis hydrogen production rete that supports of transparent commentaries on classics light rare earth silicon hydrochloric acid glass stick (diameter is 3.0mm) and surperficial Pt form jointly.With transparent commentaries on classics light rare earth silicon hydrochloric acid glass stick is sandwich layer, (is 99.99% Ta with purity through magnetron sputtering
2O
5Be raw material) and be aided with thermal treatment composite modified (ammonia flow 20mL/min, 800 ℃ the insulation 10 hours; The H of mass concentration 5%
2PtCl
6Flood 550 ℃ of down insulations 1 hour in the solution), can generating the about 480nm of thickness, Pt, to support mass ratio be 0.5% TaON photocatalysis hydrogen production rete.
" light conversion-catalysis " oxygen making reaction array (5) constitutes 3 layers up and down by bar-shaped photochemical catalysis system O compoiste material, the array of every layer 6 (as shown in Figure 4).Bar-shaped photochemical catalysis system oxygen material by the outer light-converting glass film composite material of bar-shaped transparent red (matrix: silica glass, diameter 3mm, commercially available; Film is formed: borosilicate glass, nanocrystalline YAG:25%Yb
3+, 0.2%Tm
3+Volume is 15%) support WO with surperficial Pt
3Photochemical catalysis oxygen-producing membrane layer is formed jointly.With the outer light-converting glass film composite material of bar-shaped transparent red is sandwich layer, and (with purity is that 99.0% nitric acid tungsten is raw material, through hydrolysis, film and aftertreatment in 450 ℃/1 hour becomes WO through sol-gel method
3Nanometer film) and composite modified processing (mass concentration is 5% H
2PtCl
6Flood 520 ℃ of thermal treatment 1 hour in the solution) generate thickness on the surface be that to support mass ratio be 0.45% WO for 320nm, Pt
3Photochemical catalysis oxygen-producing membrane layer.
New type solar energy photocatalytic hydrogen production by water decomposition system can obtain 83/ μ molh under sun in summer illumination
-1The hydrogen release rate.
Structure of the present invention is as shown in Figure 1: be made up of solar light collection-transmission unit, light conversion-catalyzing manufacturing of hydrogen reaction member, light conversion-catalysis oxygen making reaction unit, medium circulation control unit.
Solar light collection-transmission unit (as shown in Figure 2) is made up of Fresnel Lenses (15), condensing apparatus (16) and solar automatic tracker (17), optical fibers (2) jointly.Fresnel Lenses (15) is on condensing apparatus (16), and condensing apparatus (16) bottom connects optical fibers (2).
Light conversion-catalyzing manufacturing of hydrogen reaction member is by reactor drum tank body (A), the reaction of light conversion-catalyzing manufacturing of hydrogen array (4), reaction solution and gas separation membrane (6; 10) the common composition; Unitor (3 through light conversion-catalyzing manufacturing of hydrogen reaction array (4) port; As shown in Figure 3) with the output terminal UNICOM of solar light collection-transmission unit optical fibers (2), through the hydrogen delivery tube road (11) and the hydrogen-storing device UNICOM on reactor drum tank body (A) top.Light conversion-catalysis oxygen making reaction unit is by reactor drum tank body (B), light conversion-catalysis oxygen making reaction array (5), reaction solution and gas separation membrane (6; 10) the common composition is through the output terminal UNICOM of unitor (3) with solar light collection-transmission unit optical fibers (2).Light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of reaction medium through the medium circulation control unit.The medium circulation control unit is made up of circulating line (7,8), recycle pump (9), concentration of medium modulator jointly, and UNICOM's photocatalysis hydrogen production reaction member and photochemical catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of oxidation-reduction medium.The concentration of medium modulator is made up of flow director (12), water tank (13) and thrust-augmenting nozzle (14), realizes UNICOM through thrust-augmenting nozzle (14) and circulating line (8).Reaction medium is made up of water, sodium iodate, Soiodin jointly, and the ionic concn of iodate and iodide ion is 0.5% in the solution.Gas separation membrane (6) is a perfluoro sulfonic acid membrane, and gas separation membrane (10) is a PA membrane.
Light conversion-catalyzing manufacturing of hydrogen reaction array (4) constitutes 4 layers up and down by bar-shaped light conversion-catalyzing manufacturing of hydrogen matrix material, 6 every layer array.Bar-shaped light conversion-catalyzing manufacturing of hydrogen matrix material is by doping 2%Yb
3+And 0.1%Tm
3+The Ta that supports of transparent commentaries on classics light rare earth silicon hydrochloric acid Glass tubing (external diameter 3.0mm, internal diameter 2mm) and surperficial Pt
3N
5The photocatalysis hydrogen production rete is formed jointly.With transparent commentaries on classics light rare earth silicon hydrochloric acid glass stick is sandwich layer, (is 99.99% Ta with purity through magnetron sputtering
2O
5Be raw material) and be aided with thermal treatment composite modified (ammonia flow 20mL/min, 850 ℃ the insulation 20 hours; The H of mass concentration 8%
2PtCl
6Flood 550 ℃ of down insulations 1 hour in the solution), can generating the about 350nm of thickness, Pt, to support mass ratio be 0.6% Ta
3N
5The photocatalysis hydrogen production rete.
" light conversion-catalysis " oxygen making reaction array (5) constitutes 4 layers up and down by bar-shaped photochemical catalysis system O compoiste material, 6 every layer array.Bar-shaped photochemical catalysis system oxygen material by the outer light-converting glass film composite material of bar-shaped transparent red (matrix: quartz glass bar, diameter 3mm, commercially available; Film is formed: β-NaYF
4: 20%Yb
3+, 0.2%Tm
3+Nanocrystalline volume be borosilicate glass matrix quality 10%) with surperficial Pt support WO
3Photochemical catalysis oxygen-producing membrane layer is formed jointly.With the outer light-converting glass film composite material of bar-shaped transparent red is sandwich layer, and (with purity is that 99.0% nitric acid tungsten is raw material, through hydrolysis, film and aftertreatment in 450 ℃/1 hour becomes WO through sol-gel method
3Nanometer film) and composite modified processing (mass concentration is 5% H
2PtCl
6Flood 520 ℃ of thermal treatment 1 hour in the solution) generate thickness on the surface be that to support mass ratio be 0.45% WO for 220nm, Pt
3Photochemical catalysis oxygen-producing membrane layer.
New type solar energy photocatalytic hydrogen production by water decomposition system can obtain 68/ μ molh under sun in summer illumination
-1The hydrogen release rate.
Claims (8)
1. optically focused-commentaries on classics photorecombination enhancement type solar energy photocatalytic device for producing hydrogen through decomposing water is characterized in that: be made up of solar light collection-transmission unit, light conversion-catalyzing manufacturing of hydrogen reaction member, light conversion-catalysis oxygen making reaction unit and medium circulation control unit; Sunshine is injected into light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit through the collection and the transmission of solar light collection-transmission unit, produces with reaction medium to interact, and the photocatalysis hydrogen production reaction takes place; Wherein light conversion-catalyzing manufacturing of hydrogen reaction member is made up of the first reactor drum tank body (A), " light conversion-catalysis " hydrogen production reaction array (4), unitor (3), first gas separation membrane (6), second gas separation membrane (10) and reaction medium jointly; Solar light collection-transmission unit is made up of Fresnel Lenses (15), condensing apparatus (16) and solar automatic tracker (17), optical fibers (2) jointly; Fresnel Lenses (15) is on condensing apparatus (16); Condensing apparatus (16) bottom connects optical fibers (2); The unitor (3) of light conversion-catalyzing manufacturing of hydrogen reaction member through " light conversion-catalysis " hydrogen production reaction array port is communicated with the output terminal of solar light collection-transmission unit optical fibers (2), and the hydrogen delivery tube road (11) through first reactor drum tank body (A) top is communicated with hydrogen-storing device; Light conversion-catalysis oxygen making reaction unit is made up of the second reactor drum tank body (B), light conversion-catalysis oxygen making reaction array (5), unitor (3), first gas separation membrane (6), second gas separation membrane (10) and reaction medium jointly, and the output terminal of unitor (3) and the solar light collection-transmission unit optical fibers (2) through light conversion-catalysis oxygen making reaction array (5) port is communicated with; Light conversion-catalyzing manufacturing of hydrogen reaction member and light conversion-catalysis oxygen making reaction unit carry out the circulation exchange and the concentration regulation and control of reaction medium through the medium circulation control unit; Wherein, light conversion-catalyzing manufacturing of hydrogen reaction array (4) is made up of light conversion-catalyzing manufacturing of hydrogen matrix material, and carries out composite design as required; Light conversion-catalysis oxygen making reaction array (5) is made up of light conversion-catalysis system O compoiste material, and carries out composite design as required.
2. device for producing hydrogen according to claim 1 is characterized in that: described light conversion-catalyzing manufacturing of hydrogen matrix material and light conversion-catalysis system O compoiste material be shaped as fibrous, bar-shaped or tubulose.
3. device for producing hydrogen according to claim 1; It is characterized in that: described medium circulation control unit is made up of first circulating line (7), second circulating line (8), recycle pump (9) and concentration of medium modulator jointly; Be communicated with photocatalysis hydrogen production reaction member and photochemical catalysis oxygen making reaction unit, carry out the circulation exchange and the concentration regulation and control of oxidation-reduction medium; First circulating line (7) links from the top outlet of the first reactor drum tank body (A) and the bottom inlet of the second reactor drum tank body (B); Second circulating line (8) links from the lower part outlet of the first reactor drum tank body (A) and the upper entrance of the second reactor drum tank body (B); Wherein, The concentration of medium modulator is made up of water tank (13), thrust-augmenting nozzle (14) and flow director (12), realizes being communicated with through thrust-augmenting nozzle (14) and second circulating line (8).
4. device for producing hydrogen according to claim 1 is characterized in that: described reaction medium is made up of water and oxidation-reduction anion radical jointly; The oxidation-reduction anion radical by the ionic compound of iodine and iodate according to molar ratio 0.5～1: 1, the volumetric molar concentration of oxidation-reduction negatively charged ion in the aqueous solution is 0.1～10%; Wherein, the ionic compound of iodine is at least a kind of of Soiodin or potassiumiodide, and iodate is at least a kind of of sodium iodate or Potassium Iodate.
5. device for producing hydrogen according to claim 1 is characterized in that: described first gas separation membrane (6) is positioned at the circulating line inlet, intercepts light-catalyzed reaction product H
2And O
2Pass through; Second gas separation membrane (10) is positioned at the reaction medium top, rises to intercept H
2The effect of O; First gas separation membrane (6) is a perfluoro sulfonic acid membrane, and second gas separation membrane (10) is any one in polymeric amide or the polyimide film.
6. device for producing hydrogen according to claim 1 is characterized in that: described light conversion-catalyzing manufacturing of hydrogen matrix material changes the light sandwich layer outward by transparent red and the photocatalysis hydrogen production rete is formed; Light conversion-catalysis system O compoiste material changes the light sandwich layer outward by transparent red and photochemical catalysis oxygen-producing membrane layer is formed; Wherein, transparent red changes the light sandwich layer outward and is prepared from outer light-converting glass material of transparent red or the outer light-converting glass film composite material of transparent red; The photocatalysis hydrogen production rete is by the composite modified TaON of precious metal, Ta
3N
5, BiVO
4Or modification TiO
2In any one be prepared from; Photochemical catalysis oxygen-producing membrane layer is by the composite modified WO of precious metal
3Be prepared from; Precious metal is at least a kind of among Pt or the Ir.
7. device for producing hydrogen according to claim 6 is characterized in that: the outer light-converting glass material of described transparent red is gone up any one in silicate glass, phosphate glass or the oxyfluoride glass of changing the rare earth functional ionic for doping is infrared; The infrared conversion rare earth functional ionic of going up is by sensitized ions Yb
3+With light emitting ionic Tm
3+Or Er
3+In at least a common composition, sensitized ions Yb wherein
3+The doping molar weight is that oxide compound is formed 2～30% of mole total amount in the outer light-converting glass material of transparent red; Yb
3+: (Tm
3+And/or Er
3+) molar ratio be 0.1～5: 10.
8. device for producing hydrogen according to claim 6 is characterized in that: the outer light-converting glass film composite material of described transparent red is made up of transparent glass matrix and the outer light conversion film of transparent red jointly; Wherein, the thickness of the outer light conversion film of transparent red is 0.01～1mm; The transparent glass matrix is any one in silica glass or the silicate glass; The outer light conversion film of transparent red is by silicate or phosphate matrix and nanocrystalline NaYF4:Yb
3+, Tm
3+, NaYF4:Yb
3+, Er
3+, LiYF
4: Yb
3+, Tm
3+, LiYF
4: Yb
3+, Er
3+, YAG:Yb
3+, Tm
3+Or YAG:Yb
3+, Er
3+In at least a common composition; Nanocrystalline content is 5～30% of used silicate of the outer light conversion film of transparent red or phosphate matrix weight.
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| CN103861542A (en) * | 2012-12-18 | 2014-06-18 | 中国科学院大连化学物理研究所 | Reaction device for preparing hydrogen through solar photocatalysis |
| CN103359686B (en) * | 2013-07-15 | 2015-04-22 | 中盈长江国际新能源投资有限公司 | Light-catalyzed reaction system for collecting sunlight |
| GB201321509D0 (en) * | 2013-12-05 | 2014-01-22 | Chiverton Richard A | Combined heat power data unit and associated network apparatus systems incorporating same |
| CN104760932A (en) * | 2015-03-25 | 2015-07-08 | 水沐清源（天津）能源环境技术有限公司 | Photocatalytic water decomposition hydrogen production plant |
| CN108359115B (en) * | 2018-03-02 | 2018-12-07 | 西安文理学院 | Nafion polymer matrix Er3+/Yb3+Codope calcirm-fluoride nanocrystalline composite material and preparation method thereof |
| CN113788454B (en) * | 2021-09-29 | 2023-08-22 | 常州大学 | Solar Fresnel high-concentration hydrogen production device based on automatic light source tracking |
| CN114214080A (en) * | 2021-12-20 | 2022-03-22 | 中国矿业大学 | Biomass conversion device based on solar energy |
| CN116639650B (en) * | 2023-05-24 | 2024-01-02 | 安徽大学 | Method and system for decomposing water by photocatalysis by utilizing nonlinear spectrum conversion |
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