CN103184468A - Electrolyte solution containing tannic acid used as photosensitizing agent and photoelectrocatalytic hydrogen production system - Google Patents
Electrolyte solution containing tannic acid used as photosensitizing agent and photoelectrocatalytic hydrogen production system Download PDFInfo
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- CN103184468A CN103184468A CN 201110448145 CN201110448145A CN103184468A CN 103184468 A CN103184468 A CN 103184468A CN 201110448145 CN201110448145 CN 201110448145 CN 201110448145 A CN201110448145 A CN 201110448145A CN 103184468 A CN103184468 A CN 103184468A
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- hydrogen
- tannic acid
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 68
- 235000015523 tannic acid Nutrition 0.000 title claims abstract description 56
- 229920002258 tannic acid Polymers 0.000 title claims abstract description 56
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000001263 FEMA 3042 Substances 0.000 title claims abstract description 54
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 title claims abstract description 54
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 title claims abstract description 54
- 229940033123 tannic acid Drugs 0.000 title claims abstract description 54
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000003115 supporting electrolyte Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- 239000010405 anode material Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 150000002894 organic compounds Chemical class 0.000 claims description 27
- 125000000524 functional group Chemical group 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 229940095064 tartrate Drugs 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 208000006558 Dental Calculus Diseases 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007518 monoprotic acids Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract 1
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- 150000001875 compounds Chemical class 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000008033 biological extinction Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
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- 150000002500 ions Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LGDFHDKSYGVKDC-UHFFFAOYSA-N 8-hydroxyquinoline-5-sulfonic acid Chemical compound C1=CN=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 LGDFHDKSYGVKDC-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 206010019332 Heat exhaustion Diseases 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an electrolyte solution containing tannic acid used as a photosensitizing agent and a photoelectrocatalytic hydrogen production system using the electrolyte solution. The electrolyte solution contains an inorganic strong acid and an optional inert supporting electrolyte and is characterized by further comprising tannic acid which is used as the photosensitizing agent. The electrolyte solution containing tannic acid used as the photosensitizing agent can well improve a light absorption range of the photoelectrocatalytic hydrogen production system, thus greatly improving a hydrogen production rate and light utilization efficiency.
Description
Technical field
The present invention relates to the photoelectrocatalysis hydrogen generating system of a kind of electrolytic solution and this electrolytic solution of use, particularly, relate to and contain tannic acid as the photoelectrocatalysis hydrogen generating system of the electrolytic solution of photosensitizer and this electrolytic solution of use.
Background technology
A photoelectrocatalysis hydrogen generating system the simplest comprises light anode, negative electrode, electrolytic solution and volts DS take-off equipment.In the photoelectrocatalysis hydrogen generating system, the photon that the light anode material absorbs the specific part in the solar spectrum produces hole-electron pair, photohole generally has very strong oxidation capacity, water molecules in can direct oxidation electrolytic solution generates oxygen, light induced electron then has very strong reductibility, its by external circuit at cathode surface with the hydrogen ion (H in the electrolytic solution
+) be reduced to hydrogen.
Usually, the process of photoelectrocatalysis hydrogen manufacturing (no sacrifice agent) in the reaction of light anode and negative electrode is respectively:
The light anode:
1.SC+h=h
++ e
-Produce hole and photoelectron (this process is reversible)
2.4h
++ 2H
2O=O
2+ 4H
+Hole direct oxidation water molecules
3.O
2+ 4H
++ 4e
-=2H
2The photoelectronic side reaction of O+ heat exhaustion
SC: semiconductor catalyst (light anode material) h: illumination h
+: photohole e
-: photoelectron
Negative electrode:
4.H
++ e
-=1/2H
2Hydrogen ion in the electrolytic solution is reduced into hydrogen by photoelectron
The introducing of continuous-current plant greatly reduces the recombination rate of hole and electronics, has improved the hydrogen-producing speed of photoelectrocatalysis hydrogen generating system.Applying of external dc bias-voltage can be transferred to negative electrode rapidly with photoelectron, consumes photoelectronic side reaction in 3 thereby effectively suppressed to react the recombination rate of photohole and electronics in 1 and reacted.The introducing of continuous-current plant guarantees that just the photoelectron that has produced can be used for reducing near the negative electrode hydrogen ion to greatest extent, and the photoelectronic quantity that produces is then determined jointly by the extinction property of light anode material and the speed of semiconductor material hole drain.For a kind of definite light anode material, what of photoelectronic initial number are its absorbent properties to solar spectrum determined, a photo absorption performance is not then had in corresponding hole, if the hole can not effectively be consumed, then the photoelectron quantity that produces subsequently can significantly reduce, thereby has influenced the hydrogen-producing speed of system.The process of photohole oxidizing water molecule is very slow, and namely the speed that is consumed of hole is very slow, so the light utilising efficiency of the hydrogen generating system in the reality is very low, even is less than 1%.Therefore add in the electrolytic solution of photoelectrocatalysis hydrogen generating system that some relative water moleculess are easier can significantly to be increased the spending rate of photohole by the compound of photohole oxidation, thereby significantly improve hydrogen-producing speed and the light utilising efficiency of system.The existing organism of these compounds is organic/inorganic substance also, is collectively referred to as sacrifice agent.For any definite light anode material, its extinction scope determines that sacrifice agent just is used for consuming the hole that has produced, and it can't change the extinction scope of light anode material.The extinction scope of present light anode material mostly concentrates on the UV-light part, has only the extinction scope of a few material can reach the blue light part, then can't utilize outside the blue light part.If add suitable photosensitive compound, make its with physics or chemisorption in light anode material surface.The generation unbound electron is excited behind the photon of these compounds absorption visible parts, be injected into then on the semi-conductive conduction band, conduction band from the light anode under the effect of impressed DC voltage is transferred to the cathodic reduction hydrogen ion, so not only improve the light abstraction width of photoelectrocatalysis hydrogen generating system greatly, thereby improved hydrogen-producing speed greatly.
For example, a kind of photosensitizer with visible light spectrum scope is disclosed in the Chinese patent application 200910058202.0, oxine-5-sulfonic acid iron (III).This material formation dark green solution soluble in water has very high complex stability under meta-alkalescence or acidic conditions.In the photoelectrocatalysis hydrogen generating system, under the effect of extra electric field, this sensitizing agent obtains light induced electron at negative electrode easily and is reduced, and therefore is unfavorable for the hydrogen generation efficiency of photoelectrocatalysis hydrogen generating system.A kind of photosensitizer for dye sensitization solar battery is disclosed in the Chinese patent application 200810151310.8, triphenyl amine dyes.Triphenyl amine dyes is water insoluble, and the electrolytic solution that the photoelectrocatalysis hydrogen generating system uses is generally the aqueous solution, so triphenyl amine dyes is difficult in the photoelectrocatalysis hydrogen preparation field and is applied.
Therefore, exploitation has been conducive to improve the light abstraction width of photoelectrocatalysis hydrogen generating system, thereby the photosensitizers that has improved hydrogen-producing speed greatly is the meaningful research of carrying out this area midium or long term.
Summary of the invention
The inventor is through further investigation, find that tannic acid (tannic acid) is can enlarge the light anode material to the absorption of visible light, improve the photosensitizer of the phototranstormation efficiency of photoelectrocatalysis hydrogen generating system, Chang Gui photosensitizer is more suitable for being added in the electrolytic solution of photoelectrocatalysis hydrogen generating system relatively.For this reason, the invention provides following several aspects:
＜1 〉. a kind of electrolytic solution for the photoelectrocatalysis hydrogen generating system, comprise inorganic acid and optional inertia supporting electrolyte, described electrolytic solution contains tannic acid as photosensitizer.
＜2 〉. according to＜1〉described electrolytic solution, the mass ratio of the water in described tannic acid and the electrolytic solution is 0.1%～5%.
＜3 〉. according to＜1〉described electrolytic solution, described electrolytic solution also comprises the organism sacrifice agent.
＜4 〉. according to above-mentioned each described electrolytic solution, described organism sacrifice agent is such a kind of organic compound as sacrifice agent: have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group, and with the light anode material of described photoelectrocatalysis hydrogen generating system chemical reaction does not take place directly.
＜5 〉. according to above-mentioned each described electrolytic solution, described organism sacrifice agent comprises at least one that is selected from the and the following: monoprotic acid or monohydroxy-alcohol; Has at least one hydroxyl (OH) with at least one carboxyl (organic compound COOH); Has at least one amido (NH
2) and the organic compound of at least one carboxyl; Has at least one carbonyl (C=O) and the organic compound of at least one hydroxyl; Has at least one carbonyl (C=O) and the organic compound of at least one carboxyl; Above-mentioned any one organic salt; And above-mentioned every mixture.
＜6 〉. according to above-mentioned each described electrolytic solution for the photoelectrocatalysis hydrogen generating system, described organic sacrifice agent is at least one that is selected from the and the following: tartrate (HOOCCHOHCHOHCOOH), inferior tartrate (HOOCCOHCOOH), oxyacetic acid/glycolic acid (HOCCOOH), oxysuccinic acid (HOOCCHOHCH
2COOH), citric acid, gluconic acid, glycine (NH
2CH
2And the mixture of above-mentioned every organic compound COOH) and xitix/vitamins C.
＜7 〉. according to above-mentioned each described electrolytic solution, described inorganic acid is selected from sulfuric acid, permanganic acid, chloric acid and perchloric acid, and described inertia supporting electrolyte is selected from sodium sulfate or vitriolate of tartar.
＜8 〉. according to above-mentioned each described electrolytic solution, the concentration of wherein said inorganic acid is 0.01～1.5mol/L, and the quality of described organic sacrifice agent and the mass ratio of water are 0.5%～30%, and the concentration of described supporting electrolyte is 0～2.0mol/L.
＜9 〉. a kind of photoelectrocatalysis hydrogen generating system, described system comprises volts DS take-off equipment, light anode, negative electrode and electrolytic solution, wherein said electrolytic solution is according to above-mentioned each described electrolytic solution.
＜10 〉. tannic acid in the photoelectrocatalysis hydrogen preparation field as the purposes of photosensitizer.
Electrolytic solution of the present invention namely contains tannic acid as the electrolytic solution of photosensitizer, can improve the light abstraction width of photoelectrocatalysis hydrogen generating system well, thereby has improved hydrogen-producing speed and light utilising efficiency greatly.
Description of drawings
Fig. 1 is the molecular structure of tannic acid;
Fig. 2 is the general synoptic diagram of photoelectrocatalysis hydrogen generating system;
Fig. 3 shows and to contain in 0.08% tannic acid-0.5M sulfuric acid electrolyte system hydrogen-manufacturing reactor hydrogen output over time;
Fig. 4 shows that hydrogen output over time in the 0.5M dilute sulfuric acid electrolyte system hydrogen-manufacturing reactor;
Fig. 5 is the product hydrogen test of (1% tannic acid+5% citric acid+1% oxyacetic acid)-0.5M dilution heat of sulfuric acid under the room light condition;
Fig. 6 is the product hydrogen test of (5% citric acid+1% oxyacetic acid)-0.5M dilution heat of sulfuric acid under the room light condition; And
Fig. 7 is the product hydrogen test of (5% tannic acid+5% citric acid+1% oxyacetic acid)-0.5M dilution heat of sulfuric acid under the room light condition.
Embodiment
The invention discloses and a kind ofly contain tannic acid (tannic acid) as the electrolytic solution of photosensitizer for the photoelectrocatalysis hydrogen generating system.
Tannic acid is water-soluble, is soluble in ethanol, acetone and glycerine, and molecular structure is shown in the accompanying drawing 1.
Contain a plurality of phenolic hydroxyl groups in the tannic acid molecule, this structure makes tannic acid very sensitive to light, tannic acid can discharge a unbound electron to the conduction band of light anode material after absorbing visible light, therefore tannic acid can enlarge the light anode material to the absorption of visible light as a kind of photosensitizer, improve the phototranstormation efficiency of photoelectrocatalysis hydrogen generating system, its action principle is:
5.TA+hv
vis＝TA
++e
-
TA: tannic acid, hv
Vis: visible light e
-: unbound electron
Tannic acid can absorb a series of visible light and discharge unbound electron, and absorbing photon with the semi-conductor anode material, to produce hydrogen hole and photoelectron be two parallel processes.Tannic acid absorbs visible light and the unbound electron that discharges at first injects the conduction band of semi-conductor anode, migrate under the effect of impressed DC voltage negative electrode with near hydrogen ion be reduced to hydrogen.
As photosensitizer, tannic acid does not consume photohole, and it directly absorbs visible light and discharges a unbound electron to light anode material conduction band.This unbound electron is different from light anode material extinction and the photoelectron that inspires, but can be used for reducing near the negative electrode hydrogen ion equally.
Conventional photosensitizer or water insoluble, otherwise water-soluble but easily in cathodic reaction.And tannic acid is water-soluble, and does not have any electrode reaction, and Chang Gui photosensitizer is more suitable for being added in the electrolytic solution of photoelectrocatalysis hydrogen generating system relatively.
Of the present invention for photoelectrocatalysis hydrogen generating system electrolytic solution, the mass ratio of the water in tannic acid and the electrolytic solution is not particularly limited, in theory as long as the existence of tannic acid, can be to play photoactivated conduct, but consider from photoactivated degree, usually and the mass ratio of the water in the electrolytic solution be 0.05%～5%, optimally be 4%～5%.
Electrolytic solution of the present invention also comprises water, inorganic acid, organism sacrifice agent, perhaps Ren Xuan inertia supporting electrolyte, wherein the concentration of inorganic acid is 0.01～1.5 mol/L, the quality of organic sacrifice agent and the mass ratio of water are 0.5%～30%, and the concentration of supporting electrolyte is 0～2.0mol/L.
In the present invention, the organism sacrifice agent comprises any sacrifice agent usually used in this field, such as simple alcohols or many alcohols, and for example methyl alcohol, ethanol, glucose, simple monocarboxylic acid or polycarboxylic acid, for example formic acid, acetic acid, propanedioic acid; Or so a kind of organic compound: have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group, and described organic compound with the light anode material chemical reaction does not take place directly.
Described do not take place directly with the light anode material that chemical reaction refers to can be with light anode material, for example TiO
2Perhaps WO
3Deng, directly reduction becomes suboxide, thereby causes light anode forfeiture photoelectric catalytically active.
Described " have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group; and with the light anode material chemical reaction does not take place directly " organic compound can be selected from following in every at least one: have one or more hydroxyl simultaneously (OH) and one or more carboxyl (organic compound COOH), for example tartrate, inferior tartrate, oxyacetic acid/glycolic acid, oxysuccinic acid, citric acid, gluconic acid etc.; Has one or more amido (NH simultaneously
2) and the organic compound of one or more carboxyl, for example glycine; Has one or more carbonyl (C=O) and the organic compound of one or more hydroxyl, for example xitix/vitamins C; Above-mentioned any one organic salt; And above-mentioned every mixture.
In addition, in the present invention, the preferred organic compound that contains hydroxyl described " have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group, and with the light anode material of described photoelectrocatalysis hydrogen generating system chemical reaction does not take place directly " at least.
In addition, especially, organic compound with the reductibility that can interact to improve compound between two or more functional groups and these functional groups, such as being used in combination of at least one and tannic acid in the and the following, will bring more significant technique effect: have one or more hydroxyl simultaneously (OH) with one or more carboxyl (organic compound COOH); Has one or more amido (NH simultaneously
2) and the organism of one or more carboxyl; Has one or more carbonyl (C=O) and the organism of one or more hydroxyl.
Reason is this above-mentioned ad hoc structure that has, namely, " have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group; and chemical reaction directly do not take place with the light anode material in described organic compound ", sacrifice agent further improved the effect that consumes photohole.
Under situation about not being bound by any theory, the contriver thinks that this organic compound with ad hoc structure can be as sacrifice agent, thereby increasing substantially the hydrogen-producing speed of photoelectrocatalysis hydrogen generating system and the principle of phototranstormation efficiency is: hydroxyl and carbonyl, hydroxyl and amido, hydroxyl and carboxyl, exist very strong influencing each other between amido and the carboxyl, wherein the inducing action of hydroxyl is the strongest; There is electrophilic inductive effect in these groups, and influencing each other between the group makes the hydrogen-oxygen key in hydroxyl or the carboxyl rupture easily, that is to say that the hydrogen atom character in the hydrogen-oxygen key is more active, are dissociated into H easily
+Form corresponding negatively charged ion, the negatively charged ion of hydrogen atom wherein and the generation of dissociating is the very strong photohole of oxygen consumed voltinism directly, directly the inductive effect between the group of Xiang Lianing is the strongest, and the distance between the group is more short, and the hydrogen atom in the hydrogen-oxygen key is more active; In addition, be α carbon with the carbon that links to each other between the group, hydrogen atom becomes α hydrogen on the α carbon, and is more active than the hydrogen atom in the conventional alkyl because the inducing action α hydrogen of group also can become, thereby also is easy to react with photohole.These several factors make the organic molecule that contains corresponding group obtain activation, have strengthened the reductibility of entire compound molecule, thereby can the strong photohole of more effective oxygen consumed voltinism.
In addition, comprise one or several above-mentioned sacrifice agents hydrogen generating system phototranstormation efficiency since the adding of tannic acid can be improved on original basis, the amplitude that improves increases with the content of tannic acid, wherein the content of tannic acid reaches maximum reaching effect in 5% o'clock, increases content effect meeting again and descends.In electrolytic solution of the present invention, the effect of tannic acid is to absorb a part of visible light, and this part visible light energy is lower, can't inspire photoelectron at the light anode material, and tannic acid can absorb this part visible light, discharge unbound electron, this effect is the absorption of widening sunlight spectrum.
In the present invention, described inorganic acid refers to the mineral acid of ionization constant pKa≤0 in the aqueous solution, for example, can comprise sulfuric acid, permanganic acid, chloric acid or perchloric acid.
Inertia supporting electrolyte in the electrolytic solution described in the present invention refers to not take place any reaction in the photoelectrocatalysis hydrogen production process, but can effectively improve a kind of compound or several compound of the specific conductivity of electrolytic solution in the photoelectrocatalysis hydrogen generating system, for example sodium sulfate, vitriolate of tartar.
A second aspect of the present invention provides a kind of system for photoelectrocatalysis hydrogen manufacturing, described system comprises the volts DS take-off equipment, the light anode, negative electrode and electrolytic solution, wherein said electrolytic solution is to comprise tannic acid as the electrolytic solution of photosensitizer, preferably comprise tannic acid and sacrifice agent as photosensitizer, especially so a kind ofly have the organic compound of ad hoc structure as the electrolytic solution of sacrifice agent: have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group, and described organic compound with the light anode material chemical reaction does not take place directly.
On the other hand, the invention discloses tannic acid purposes as photosensitizer in the photoelectrocatalysis hydrogen preparation field.
Below explain electrolytic solution provided by the present invention in detail by specific embodiment, embodiment only is used for further specifying the present invention, rather than limits the scope of the invention.
Embodiment
[embodiment 1]
Present embodiment is used for illustrating that electrolytic solution among the present invention is to photoelectrocatalysis hydrogen generating system hydrogen-producing speed and the remarkable promoter action of light utilising efficiency
(1) uses beaker to measure 8 milliliters of the vitriol oils, move in 500 ml beakers, use deionized water to be diluted to 300 milliliters with the dilution heat of sulfuric acid of configuration 0.5mol/L.
(2) taking by weighing 0.24 gram tannic acid is dissolved to and is mixed with final electrolytic solution in the dilution heat of sulfuric acid.
(3) will dispose about 300 milliliters of electrolytic solution of finishing moves in the airtight synthetic glass photoelectrocatalysis hydrogen-manufacturing reactor.
(4) WO for preparing with coating method (Chinese patent application 201010269960.x or Chinese patent application 201010269963.3)
3As the light anode material, actual light-receiving area is 9cm
2With smooth platinized platinum as cathode material; Light source is sunlight, and sun light intensity uses luxmeter (Taiwan safe bodyguard TES TES 1330A) to measure; (the special CS350 of Instr Ltd. of Wuhan Cohan) provides 1.2V direct-current biasing by the CS3500 electrochemical workstation, and records the variation of whole process electric current to the time; Extract 0.2 milliliter gas from the cathode terminal of hydrogen-manufacturing reactor with pin with lock (U.S. Agilent manufacturing) every about 1 hour or half an hour, with the output of hydrogen in Agilent 6820 gas-chromatographies (the Agilent6820 type gas spectrum that U.S. Agilent produces) the test hydrogen-manufacturing reactor.Hydrogen output is carried out least square fitting to the data of time obtain straight line, the slope of this fitting a straight line is hydrogen-producing speed; Phototranstormation efficiency (η) adopts following formula to calculate:
Wherein: Δ G
0: 237 * 10
3J/mol
: hydrogen-producing speed (mol/s)
E: light intensity (W/cm
2)
A: illuminating area (cm
2)
Sacrifice agent is to the influence of hydrogen-manufacturing reactor total system in use hydrogen-producing speed and these two parameter evaluation electrolytic solution of phototranstormation efficiency.
(5) place of outdoor sunlight test is at Hebei province's Langfang City (116.74 ° of east longitudes, 39.60 ° of north latitude), and the test duration is 11:00AM-2:00PM, and the sunlight intensity of using luxmeter to measure is 45mW/cm
2Mean current in the test process is 5.04mA; Hydrogen-producing speed is 0.149mmol/h as shown in Figure 3; Can get phototranstormation efficiency (η) by following formula is 0.93%.
[Comparative Examples 1]
Except sun light intensity is 60mW/cm
2Outside, the electrolytic solution that uses in the Comparative Examples 1 is the 0.5M dilute sulphuric acid.Whole test process is with shown in the embodiment 1, and the mean current of acquisition is 4.42mA.Hydrogen-producing speed is 0.132mmol/h as shown in Figure 4, and phototranstormation efficiency is 0.63%.
Above-described embodiment 1 and Comparative Examples 1 have confirmed, even under the situation of not using any sacrifice agent, use tannic acid that hydrogen-producing speed and the phototranstormation efficiency of system also can be provided separately, have confirmed that tannic acid can be used as the purposes of photosensitizers.
[embodiment 2]
(1) measures 300 milliliters of 0.5M dilution heat of sulfuric acid; Take by weighing 3.0 gram tannic acid solids; Take by weighing 15.74 gram citric acid solids; Take by weighing 3.15 gram oxyacetic acid/glycolic acid liquid; And tannic acid, citric acid and oxyacetic acid be dissolved to be made into the 0.5M dilution heat of sulfuric acid that contains (1% tannic acid+5% citric acid+1% oxyacetic acid) in the dilution heat of sulfuric acid.The 0.5M dilution heat of sulfuric acid that disposes about 300 milliliters (1% tannic acids+5% citric acid+1% oxyacetic acid) finishing is moved in the airtight synthetic glass photoelectrocatalysis hydrogen-manufacturing reactor.
(2) WO for preparing with coating method (Chinese patent application 201010269960.x or Chinese patent application 201010269963.3)
3As the light anode material, actual light-receiving area is 9cm
2With smooth platinized platinum as cathode material.
(3) provide 1.2V direct-current biasing by the CS3500 electrochemical workstation, and record the variation of whole process electric current to the time; Extract 0.2 milliliter gas from the cathode terminal of hydrogen-manufacturing reactor with pin with lock (U.S. Agilent manufacturing) every about half an hour, with the output of hydrogen in Agilent 6820 gas-chromatographies (the Agilent6820 type gas spectrum that U.S. Agilent produces) the test hydrogen-manufacturing reactor.
(4) hydrogen output is carried out least square fitting to the data of time and obtain straight line, the slope of this fitting a straight line is hydrogen-producing speed.
(5) freely opening up the PLS-SXE300 xenon lamp that Science and Technology Ltd. produces with Beijing is the simulated solar light source, measures with luxmeter, and its light intensity is transferred to 100mW/cm
2With the UV-CUTOFF spectral filter UV-light is partly filtered, only keep visible light part and infrared light part in this analog light source; Regulate distance and height between xenon lamp and the light anode material, guarantee that hot spot just in time drops on the center of light anode material, so that light anode material material is subjected to light even.
(6) consistent among phototranstormation efficiency method of calculation and the front embodiment 1.Hydrogen-producing speed is 1.0 mmol/h as shown in Figure 5.This time the mean current that obtains in the test is 25.40mA.It is 3.9% that calculating can get phototranstormation efficiency.
[Comparative Examples 2]
Except not containing 1% tannic acid, the electrolytic solution that uses in the Comparative Examples 2 is the 0.5M dilution heat of sulfuric acid of (5% citric acid+1% oxyacetic acid).The mean current that obtains in the whole test process is 23.12mA.Hydrogen-producing speed is 0.90mmol/h as shown in Figure 6, and phototranstormation efficiency is 3.5%.
The presentation of results of embodiment 2 and Comparative Examples 2 sacrifice agent and tannic acid being used in combination in the photoelectricity hydrogen generating system, can further improve hydrogen-producing speed and the phototranstormation efficiency of system.
[embodiment 3]
(1) measures 300 milliliters of 0.5M dilution heat of sulfuric acid; Take by weighing 15.0 gram tannic acid solids; Take by weighing 15.74 gram citric acid solids; Take by weighing 3.15 gram oxyacetic acid/glycolic acid liquid; And tannic acid, citric acid and oxyacetic acid be dissolved to be made into the 0.5M dilution heat of sulfuric acid that contains (5% tannic acid+5% citric acid+1% oxyacetic acid) in the dilution heat of sulfuric acid.The 0.5M dilution heat of sulfuric acid that disposes about 300 milliliters (5% tannic acids+5% citric acid+1% oxyacetic acid) finishing is moved in the airtight synthetic glass photoelectrocatalysis hydrogen-manufacturing reactor.
(2) WO for preparing with high-temperature sintering process and coating method
3As the light anode material, actual light-receiving area is 9cm
2With smooth platinized platinum as cathode material.
(3) provide 1.2V direct-current biasing by the CS3500 electrochemical workstation, and record the variation of whole process electric current to the time; Extract 0.2 milliliter gas from the cathode terminal of hydrogen-manufacturing reactor with pin with lock (U.S. Agilent manufacturing) every about half an hour, with the output of hydrogen in Agilent 6820 gas-chromatographies (the Agilent6820 type gas spectrum that U.S. Agilent produces) the test hydrogen-manufacturing reactor.
(4) hydrogen output is carried out least square fitting to the data of time and obtain straight line, the slope of this fitting a straight line is hydrogen-producing speed.
(5) freely opening up the PLS-SXE300 xenon lamp that Science and Technology Ltd. produces with Beijing is the simulated solar light source, measures with luxmeter, and its light intensity is transferred to 100mW/cm
2With the UV-CUTOFF spectral filter UV-light is partly filtered, only keep visible light part and infrared light part in this analog light source; Regulate distance and height between xenon lamp and the light anode material, guarantee that hot spot just in time drops on the center of light anode material, so that light anode material material is subjected to light even.
(6) consistent among phototranstormation efficiency method of calculation and the front embodiment 1.Hydrogen-producing speed is 1.19 mmol/h as shown in Figure 7.This time the mean current that obtains in the test is 29.30mA.It is 4.8% that calculating can get phototranstormation efficiency
The presentation of results of embodiment 3, even using under the situation of simulated solar irradiation as light source, use this combination of the present invention to contain tannic acid and have the system of electrolytic solution of the sacrifice agent of ad hoc structure, also can significantly improve hydrogen-producing speed and the phototranstormation efficiency of system.
Industrial applicability
Because electrolytic solution of the present invention can increase substantially hydrogen-producing speed and the phototranstormation efficiency of photoelectro catalytic system, therefore be particularly suitable for in industrial use.
Claims (10)
1. an electrolytic solution that is used for the photoelectrocatalysis hydrogen generating system comprises inorganic acid and optional inertia supporting electrolyte, it is characterized in that also comprising tannic acid as photosensitizer.
2. electrolytic solution according to claim 1, the mass ratio of the water in described tannic acid and the electrolytic solution is 0.1%～5%.
3. electrolytic solution according to claim 1, described electrolytic solution also comprises the organism sacrifice agent.
4. electrolytic solution according to claim 3, described organism sacrifice agent is such a kind of organic compound as sacrifice agent: have the reductibility that can interact to strengthen described organic compound between two or more functional groups and the described functional group, and with the light anode material of described photoelectrocatalysis hydrogen generating system chemical reaction does not take place directly.
5. electrolytic solution according to claim 4, described organism sacrifice agent comprise and are selected from following in every at least one: monoprotic acid or monohydroxy-alcohol; Organic compound with at least one hydroxyl and at least one carboxyl; Organic compound with at least one amido and at least one carboxyl; Organic compound with at least one carbonyl and at least one hydroxyl; Above-mentioned any one organic salt; And above-mentioned every mixture.
6. the electrolytic solution for photochemical catalysis or photoelectrocatalysis hydrogen generating system according to claim 5, described organic sacrifice agent is to be selected from following in every at least one: tartrate, inferior tartrate, oxyacetic acid/glycolic acid, oxysuccinic acid, citric acid, gluconic acid, glycine and xitix/vitamins C, and the mixture of above-mentioned every organic compound.
7. according to each described electrolytic solution among the claim 1-6, described inorganic acid is selected from sulfuric acid, permanganic acid, chloric acid and perchloric acid, and described inertia supporting electrolyte is selected from sodium sulfate or vitriolate of tartar.
8. according to each described electrolytic solution among the claim 1-7, the concentration of wherein said inorganic acid is 0.01～1.5mol/L, and the quality of described organic sacrifice agent and the mass ratio of water are 0.5%～30%, and the concentration of described supporting electrolyte is 0～2.0mol/L.
9. photoelectrocatalysis hydrogen generating system, described system comprises volts DS take-off equipment, light anode, negative electrode and electrolytic solution, wherein said electrolytic solution is according to each described electrolytic solution in the claim 1 to 8.
Tannic acid in the photoelectrocatalysis hydrogen preparation field as the purposes of photosensitizer.
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| CN108722395A (en) * | 2018-06-25 | 2018-11-02 | 北方民族大学 | A kind of platinum nano catalyst and its hydrogen production process prepared using vinifera residue |
| CN109081305A (en) * | 2018-08-16 | 2018-12-25 | 陕西师范大学 | A kind of method of while biomass degradation and light degradation aquatic products hydrogen |
| CN113060702A (en) * | 2021-03-19 | 2021-07-02 | 扬州大学 | Method for efficiently utilizing organic sacrificial agent in hydrogen production by photocatalytic water decomposition |
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| CN108722395A (en) * | 2018-06-25 | 2018-11-02 | 北方民族大学 | A kind of platinum nano catalyst and its hydrogen production process prepared using vinifera residue |
| CN109081305A (en) * | 2018-08-16 | 2018-12-25 | 陕西师范大学 | A kind of method of while biomass degradation and light degradation aquatic products hydrogen |
| CN113060702A (en) * | 2021-03-19 | 2021-07-02 | 扬州大学 | Method for efficiently utilizing organic sacrificial agent in hydrogen production by photocatalytic water decomposition |
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