CN105728048A - Artificial photosynthesis system and application thereof - Google Patents
Artificial photosynthesis system and application thereof Download PDFInfo
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- CN105728048A CN105728048A CN201610064732.6A CN201610064732A CN105728048A CN 105728048 A CN105728048 A CN 105728048A CN 201610064732 A CN201610064732 A CN 201610064732A CN 105728048 A CN105728048 A CN 105728048A
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- artificial photosynthesis
- enzyme
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- melamine
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- 238000004577 artificial photosynthesis Methods 0.000 title claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 102000004190 Enzymes Human genes 0.000 claims abstract description 27
- 108090000790 Enzymes Proteins 0.000 claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 15
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 229940044927 ceric oxide Drugs 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 238000013019 agitation Methods 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses an artificial photosynthesis system and an application thereof. The artificial photosynthesis system comprises an artificial enzyme carrier, a light capture agent and an artificial enzyme, wherein the artificial enzyme comprises a coordination compound formed by metal ions and more than two nitrogen-atoms in melamine molecule in the artificial enzyme carrier. The artificial photosynthesis system contains 0.5-6wt% of melamine. The artificial photosynthesis system provided by the invention takes the melamine as the photosensitizer and the artificial enzyme carrier and the coordination compound formed between metal ions and nitrogen-atoms as the artificial enzyme, so that the selectivity of the photocatalytic reduction products to methyl alcohol is increased. The artificial photosynthesis system provided by the invention puts forward taking the semiconductor material ceric oxide coupling metal complex as the artificial enzyme for constructing a theoretical model for the artificial photosynthesis system, so that the applications of the semiconductor material CeO2 and melamine in the photocatalysis field are widened, the photocatalyst preparation process according to the invention is simple and the raw materials are low-cost and easily acquired.
Description
Technical field
The present invention relates to the structure of a kind of artificial photosynthesis's system and application, belong to photocatalysis technology field.
Background technology
Solar energy is green energy resource, to environment without polluting, under room temperature, normal pressure, by CO in aqueous solution2Photo catalytic reduction is HCOOH, CH3The Organic substances such as OH, have opened up the new way utilizing Solar use.TiO2Photo catalytic reduction CO2Reduzate there is no selectivity, be generally the mixture of several compound such as carbon monoxide, methane, its productivity is low, and TiO2The visible ray in solar energy can not be effectively utilized.Especially gaseous matter is both not easy to store, and is also not easy to application.Therefore, it is that the fuel molecule being in a liquid state under normal temperature and pressure has actual using value by carbon dioxide photo catalytic reduction.
Cerium oxide is a kind of light rare earth semi-conducting material, its can band can artificial regulatory within the scope of 2.64-3.00eV.Additionally, the Graphene of rising in recent years is also a kind of semi-conducting material, its band gap is zero.The band structure of cerium oxide can be regulated and controled by graphene oxide and cerium oxide-doped, increase the response to visible ray, improve the utilization rate to solar energy, but by low for selectivity that carbon dioxide photo catalytic reduction is methanol in prior art, and photocatalysis product is complicated.
Summary of the invention
For the deficiencies in the prior art, present invention is primarily targeted at a kind of artificial photosynthesis's system of offer and application thereof.
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
In some embodiments provide a kind of artificial photosynthesis's system to include:
Artificial enzyme's carrier, including the tripolycyanamide being used as photosensitizer,
Light trapping agent, including cerium oxide,
And, artificial enzyme, including the coordination compound formed with the two or more nitrogen-atoms in the melamine molecule in described artificial enzyme's carrier by metal ion.
In some embodiments provide a kind of method preparing above-mentioned artificial photosynthesis's system to include: solubility cerium salt and alkali liquor are mixed to and be precipitated as glassy yellow, mixing with the pH value melamine solution more than 10 afterwards and be placed in hermetic container and react 6-8h when 100-200 DEG C, loaded metal ion prepares described artificial photosynthesis's system afterwards.
A kind of method that carbon dioxide photo catalytic reduction is prepared methanol includes in certain embodiments: above-mentioned artificial photosynthesis's system, reducing agent and the stirring of solubility bicarbonate prepare mixed liquor, is placed in Photoreactor by mixed liquor illumination afterwards.
Compared with prior art, the invention have the advantages that
(1) a kind of artificial photosynthesis's system of the present invention is with CeO2For light trapping agent, with tripolycyanamide for photosensitizer and artificial enzyme's carrier, with the coordination compound that formed between metal ion and nitrogen-atoms for artificial enzyme.Additionally, the lone pair electrons complexation Cu of nitrogen-atoms in tripolycyanamide2+, increase photo catalytic reduction CO2Assosting effect, add the photo catalytic reduction product methanol selectivity to easily storage, and methanol content be higher.
(2) a kind of artificial photosynthesis's system of the present invention proposes semi-conducting material ceria coupling metal complex and builds the theoretical model of artificial photosynthetic systems as artificial enzyme, thus having widened semi-conducting material CeO2With the tripolycyanamide application in photocatalysis field, the photocatalyst preparation process of the present invention is simple, and raw material is cheap and easy to get.
Accompanying drawing explanation
Fig. 1 is the reaction mechanism figure in the present invention one comparatively specific embodiment；
Fig. 2 is ceria (CeO in the embodiment of the present invention 12), tripolycyanamide ((NH2)3C3N3) and CeO 2 supporting tripolycyanamide (CeO2-g-C3N4) X-ray diffractogram；
Fig. 3 is ceria (CeO in the embodiment of the present invention 12), tripolycyanamide ((NH2)3C3N3) and CeO 2 supporting tripolycyanamide (CeO2-g-C3N4) diffuse-reflectance collection of illustrative plates.
Detailed description of the invention
In view of deficiency of the prior art, inventor, through studying for a long period of time and putting into practice in a large number, is proposed technical scheme.This technical scheme, its implementation process and principle etc. will be further explained as follows.
Principles of the invention is with CeO2For light trapping agent, with tripolycyanamide for photosensitizer and artificial enzyme's carrier, so that between metal ion and described tripolycyanamide, the coordination compound of formation is for artificial enzyme, successfully constructing can by CO2Photo catalytic reduction is artificial photosynthesis's system of methanol.As nano Ce O2-NG granule is at copper ion (Cu2+) ultrasonic in solution time, copper ion and nitrogen-atoms complexation be:
When illumination vitalizing semiconductor, creating light induced electron and photohole, the existence of copper ion reduces the compound of light induced electron and photohole, and by copper ion, light induced electron is transferred to CO2Being reduced to methanol on molecule, photohole is constantly by SO3 2-Ion consumes.Concrete equation is as follows:
CO2(g)+6H++6e-→CH3OH(aq)+H2O(1)
SO3 2-+h+→SO4 2-(2)
Its reaction mechanism is represented by shown in lower Fig. 1.
In some embodiments provide a kind of artificial photosynthesis's system to include:
Artificial enzyme's carrier, including the tripolycyanamide being used as photosensitizer,
Light trapping agent, including cerium oxide,
And, artificial enzyme, including the coordination compound formed with the two or more nitrogen-atoms in the melamine molecule in described artificial enzyme's carrier by metal ion.
Comparatively preferred, described metal ion includes Cu2+Or Ni2+In the combination of any one or two kinds, but be not limited to this.
Comparatively preferred, described artificial photosynthesis's system comprises 0.5-6wt% tripolycyanamide.
Comparatively preferred, described cerium oxide is graininess, and described cerium oxide is distributed in the layer structure of described artificial enzyme's carrier surface or described artificial enzyme's carrier.
In some embodiments provide a kind of method preparing above-mentioned artificial photosynthesis's system to include: solubility cerium salt and alkali liquor are mixed to and be precipitated as glassy yellow, mixing with the pH value melamine solution more than 10 afterwards and be placed in hermetic container and react 6-8h when 100-200 DEG C, loaded metal ion prepares described artificial photosynthesis's system afterwards.
Comparatively preferred, described solubility cerium salt includes the combination of any one or two kinds in cerium chloride, cerous sulfate, but is not limited to this.
Comparatively preferred, described alkali liquor includes sodium hydroxide solution, but is not limited to this.
Comparatively preferred, described metal ion includes the combination of any one or two kinds in nickel ion, copper ion, but is not limited to this.
Comparatively preferred, use sodium hydroxide solution to regulate the pH value of tripolycyanamide mixed solution more than 10.
A kind of method that carbon dioxide photo catalytic reduction is prepared methanol includes in certain embodiments: above-mentioned artificial photosynthesis's system, reducing agent and the stirring of solubility bicarbonate prepare mixed liquor, is placed in Photoreactor by mixed liquor illumination afterwards.
Comparatively preferred, it is the light source of 200-500nm that described Photoreactor includes launching wavelength, and light application time is 60-100min.
Comparatively preferred, the mass ratio of described artificial photosynthesis's system, reducing agent and solubility bicarbonate is 1:10-30:50-70,
Comparatively preferred, described reducing agent includes sodium sulfite.
Comparatively preferred, described solubility bicarbonate includes the combination of any one or two kinds in sodium bicarbonate, potassium bicarbonate.
Below in conjunction with drawings and Examples, the technological invention of the present invention is further explained.
Embodiment 1
(1) preparation of tripolycyanamide aza-titanium oxide cerium: by CeCl3·7H2O (1.0000g, 0.0.0027mol) it is dissolved in 20mL distilled water magnetic agitation to dissolving, regulating mixed liquor pH value by NaOH solution (1.0mol/L, 10mL) afterwards > 10 magnetic agitation obtain mixed liquor A to being precipitated as glassy yellow, then by (NH2)3C3N3(1.0000g, 99%) is dissolved in NaOH solution (0.1mol/L, 10mL) solution and disperses ultrasonic 2h to obtain mixed liquid B.Being added drop-wise in mixed liquor A by mixed liquid B under magnetic agitation magnetic agitation 30min, ultrasonic 3h prepares complex liquid.Then being added by complex liquid solution in the hydrothermal reaction kettle of 100ml, be placed in when 180 DEG C after reaction 6h, filtration, washing, in vacuum drying oven, dry (50 DEG C, 6h) prepare tripolycyanamide aza-titanium oxide cerium (CeO2-g-C3N4)。
(2) load of artificial enzyme: by CuSO4·5H2O (0.2000g, 0.0008mol) is dissolved in 20mL distilled water, is configured to CuSO4·5H2O solution (100mL, 0.008mol/L), measures CuSO afterwards4·5H2O (10mL, 0.008mol/L) and CeO2-g-C3N4(0.1000g) magnetic agitation 30min, by ultrasonic for mixed liquor 5h, filters, washing, and vacuum drying oven dries (60 DEG C, 6h) and prepares the composite photo-catalyst of copper ion Supported Melamine aza-titanium oxide cerium and above-mentioned artificial photosynthesis's system.
(3) photo catalytic reduction CO2Experiment: use CO2Bubbling is dissolved in 0.1mol/LNaHCO to remove in 20 minutes3Dissolved oxygen in solution, adds the Na of 0.1mol/L2SO3After be separately added into the above-mentioned composite photo-catalyst of 0.1g, light-catalyzed reaction 80min, take 1mL every 20min and be centrifuged, the content of methanol in detection solution, Xe light is according to 80min, and the productivity recording methanol is 257.22 μm of ol g-1cat.·h-1。
Embodiment 2
(1) preparation of tripolycyanamide aza-titanium oxide cerium: by CeCl3·7H2O (1.0000g, 0.0.0027mol) it is dissolved in 20mL distilled water magnetic agitation to dissolving, regulating mixed liquor pH value by NaOH solution (1.0mol/L, 10mL) afterwards > 10 magnetic agitation obtain mixed liquor A to being precipitated as glassy yellow, then by (NH2)3C3N3(1.0000g, 99%) is dissolved in NaOH solution (0.1mol/L, 10mL) solution and disperses ultrasonic 2h to obtain mixed liquid B.Being added drop-wise in mixed liquor A by mixed liquid B under magnetic agitation magnetic agitation 30min, ultrasonic 3h prepares complex liquid.Then being added by complex liquid solution in the hydrothermal reaction kettle of 100ml, be placed in when 180 DEG C after reaction 6h, filtration, washing, in vacuum drying oven, dry (50 DEG C, 6h) prepare tripolycyanamide aza-titanium oxide cerium (CeO2-g-C3N4)。
(2) load of artificial enzyme: by NiSO4(0.2000g, 0.0008mol) is dissolved in 20mL distilled water, is configured to NiSO4·5H2O solution (100mL, 0.008mol/L), measures NiSO afterwards4·5H2O (10mL, 0.008mol/L) and CeO2-g-C3N4(0.1000g) magnetic agitation 30min, by ultrasonic for mixed liquor 5h filter, washing, vacuum drying (60 DEG C, 6h) prepare nickel ion Supported Melamine aza-titanium oxide cerium composite photo-catalyst, i.e. above-mentioned artificial photosynthesis's system.
(3) photo catalytic reduction CO2Experiment: use CO2Bubbling is dissolved in 0.1mol/LNaHCO to remove in 20 minutes3Dissolved oxygen in solution, adds the Na of 0.1mol/L2SO3After be separately added into the above-mentioned composite photo-catalyst of 0.1g, light-catalyzed reaction 80min, take 1mL every 20min and be centrifuged, the content of methanol in detection solution, Xe light is according to 80min, and the productivity recording methanol is 227.15 μm of ol g-1cat.·h-1。
Above example adopt gas chromatograph (model AgilentTechnologies7890B) detect the content of wherein methanol.Utilize 250WXe lamp as light source, photo catalytic reduction CO2Carrying out in photocatalytic reactors (model BL-GHX-V, Shanghai is than youth Instrument Ltd.), maintaining temperature is (25 DEG C ± 2 DEG C), and the temperature keeping reaction system with fridge recirculated water is steady state value.
The measuring method of methanol: first set up a standard working curve by gas chromatogram, the standard solution of compounding methanol respectively, quality solubility respectively one thousandth, ten thousand/, 1 1/1000000th/100000ths, adopt the peak area of methanol in gas chromatograph measurement standard solution respectively, make standard curve.The appearance time of methanol is 1.698, after photocatalysis the methanol content of solution close to 100,000/, adopt the method for analogy to measure the content of methanol in solution.
Should be appreciated that above-described embodiment is only the technology design and feature that the present invention is described, its object is to allow person skilled in the art will appreciate that present disclosure and to implement according to this, can not limit the scope of the invention with this.All equivalences made according to spirit of the invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. artificial photosynthesis's system, it is characterised in that including:
Artificial enzyme's carrier, including the tripolycyanamide being used as photosensitizer,
Light trapping agent, including cerium oxide,
And, artificial enzyme, including the coordination compound formed with the two or more nitrogen-atoms in the melamine molecule in described artificial enzyme's carrier by metal ion.
2. artificial photosynthesis's system according to claim 1, it is characterised in that: described metal ion includes Cu2+Or Ni2+In the combination of any one or two kinds.
3. artificial photosynthesis's system according to claim 1, it is characterised in that: described artificial photosynthesis's system comprises 0.5～6wt% tripolycyanamide.
4. artificial photosynthesis's system according to claim 1, it is characterised in that: described cerium oxide is graininess, and described cerium oxide is distributed in the layer structure of described artificial enzyme's carrier surface or described artificial enzyme's carrier.
5. the method for the artificial photosynthesis's system prepared in claim 1-4 described in any one, it is characterized in that including: solubility cerium salt and alkali liquor are mixed to and be precipitated as glassy yellow, mixing with the pH value melamine solution more than 10 afterwards and be placed in hermetic container and react 6-8h when 100-200 DEG C, loaded metal ion prepares described artificial photosynthesis's system afterwards.
6. preparation method according to claim 5, it is characterised in that: described solubility cerium salt includes the combination of any one or two kinds in cerium chloride, cerous sulfate.
7. preparation method according to claim 5, it is characterised in that: described alkali liquor includes sodium hydroxide solution,
And/or, described metal ion includes the combination of any one or two kinds in nickel ion, copper ion.
8. the method that carbon dioxide photo catalytic reduction is prepared methanol, it is characterized in that including: the stirring of the artificial photosynthesis's system described in any one in claim 1-4, reducing agent and solubility bicarbonate is prepared mixed liquor, is placed in Photoreactor by mixed liquor illumination afterwards.
9. a kind of method that carbon dioxide photo catalytic reduction is prepared methanol according to claim 8, it is characterised in that: it is the light source of 200-500nm that described Photoreactor includes launching wavelength, and light application time is 60-100min.
10. a kind of method that carbon dioxide photo catalytic reduction is prepared methanol according to claim 8, it is characterised in that: the mass ratio of described artificial photosynthesis's system, reducing agent and solubility bicarbonate is 1:10-30:50-70,
And/or, described reducing agent includes sodium sulfite,
And/or, described solubility bicarbonate includes the combination of any one or two kinds in sodium bicarbonate, potassium bicarbonate.
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