CN105688885A - Composite photocatalyst GO@CexEryO2 and preparation method and application thereof - Google Patents
Composite photocatalyst GO@CexEryO2 and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 150000000917 Erbium Chemical class 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 239000008187 granular material Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 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
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 abstract description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- 239000013049 sediment Substances 0.000 abstract description 3
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- -1 Oxygen ion Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052691 Erbium Inorganic materials 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005169 Debye-Scherrer Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a composite photocatalyst GO@CexEryO2 and a preparation method and application thereof. The composite pohtocatalyst comprises layered graphene oxide and CexEryO2 granules distributed on the surface of the graphene oxide, wherein the value range of x in CexEryO2 is larger than zero and smaller than one, the value range of y is larger than 0.01 and smaller than 1, and the forbidden bandwidth of the composite photocatalyst ranges from 3.16 eV to 2.65 eV. The preparation method of the composite photocatalyst comprises the steps that soluble cerium salt and soluble erbium salt are dissolved and mixed with an alkaline solution, stirring is conducted till sediment is luminous yellow, mixed liquor is obtained and mixed with a graphene oxide suspension, and a hydrothermal reaction is conducted. According to the composite photocatalyst, after graphene oxide is adopted to modify cerium oxide, absorption spectra are subjected to red shift, the utilization rate to solar energy is increased, the preparation process is simple, and the yield of a prepared reduction product methyl alcohol is higher.
Description
Technical field
The present invention relates to a kind of photocatalyst, particularly to a kind of composite photo-catalyst GOCexEryO2, its preparation method and photocatalytic reduction of carbon oxide be methanol, belong to photocatalysis technology field。
Background technology
In recent years, solar energy photocatalytic reduction carbon dioxide is utilized to have become as the focus of research for the little molecule of organic-fuel。TiO2It is a kind of common photocatalyst, it is possible to by CO2Photo catalytic reduction is organic-fuel molecule。But TiO2Ultraviolet light can only be absorbed, therefore that the utilization rate of solar energy is relatively low。CeO2Being a kind of rare earth metal oxide semi-conducting material, its Lattice Oxygen ion easily lacks, and causes CeO2Electron concentration in crystal is higher, it is easy to form Ce3+。The character of this uniqueness makes the band structure more easy-regulating of cerium oxide, therefore this semi-conducting material and TiO2Compare and there is higher solar energy utilization ratio, faster electron transfer rate, less hole/electronics recombination rate, higher photocatalytic activity。But, pure CeO2Band gap relatively larger, the visible ray utilization rate in solar energy is extremely limited, it is therefore necessary to it is modified。
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of composite photo-catalyst GOCexEryO2, its preparation method and application。
For realizing aforementioned invention purpose, the technical solution used in the present invention includes:
In some embodiments providing a kind of composite photo-catalyst, described composite photo-catalyst includes the graphene oxide of stratiform and is distributed in the Ce of described surface of graphene oxidexEryO2Granule, wherein said CexEryO2The span of middle x is the span of 0 < x < 1, y is 0.01 < y < 1, and the energy gap of described composite photo-catalyst is 3.16-2.65eV。
The preparation method in some embodiments providing a kind of above-mentioned composite photo-catalyst includes: by solubility cerium salt, solubility erbium salt dissolves and alkaline solution mixes to and is precipitated as glassy yellow, obtain after mixed liquor mixes with graphene oxide suspension hydro-thermal reaction 8-6h at 160-180 DEG C, prepare described composite photo-catalyst。
In some embodiments provide above-mentioned composite photocatalyst material in photocatalysis carbon dioxide be the application in methanol。
Compared with prior art, the invention have the advantages that
(1) composite photo-catalyst of the present invention, including graphene oxide and the Ce being distributed in described surface of graphene oxide of stratiformxEryO2Granule, described CexEryO2The energy gap of granule is 3.15-2.75eV, after combined oxidation Graphene, the energy gap of described composite photo-catalyst is further reduced to 2.65eV, cause absorption spectrum Einstein shift, increase the utilization rate to solar energy, and the addition of graphene oxide has further speeded up the separation of light induced electron and photohole pair in light-catalyzed reaction process, improving photocatalytic reduction of carbon oxide is the productivity of methanol。
(2) preparation method of the composite photo-catalyst of the present invention, graphene oxide suspension is adopted to replace traditional noble metal, save cost, and photocatalyst preparation process is simple, prepares photocatalyst the selectivity that photocatalytic reduction of carbon oxide is methanol is higher。
Accompanying drawing explanation
Fig. 1 is the reaction mechanism figure in the present invention one comparatively specific embodiment；
Fig. 2 a is the transmission electron microscope picture of graphene oxide in the embodiment of the present invention 1, and Fig. 2 b-Fig. 2 d is graphene oxide compound Er ions cerium oxide (GOCe under different scale in the embodiment of the present invention 1xEryO2) transmission electron microscope picture；
Fig. 3 is cerium oxide (CeO in the embodiment of the present invention 12), Er ions cerium oxide (CexEryO2) and graphene oxide compound Er ions cerium oxide (GOCexEryO2) Raman collection of illustrative plates；
Fig. 4 is cerium oxide (CeO in the embodiment of the present invention 12), Er ions cerium oxide (CexEryO2) and graphene oxide compound Er ions cerium oxide (GOCexEryO2) the spectrogram that diffuses；
Fig. 5 is graphene oxide compound Er ions cerium oxide (GOCe in the embodiment of the present invention 2xEryO2) XPS width scanning spectrogram；
Fig. 6 is cerium oxide (CeO in the embodiment of the present invention 22), Er ions cerium oxide (CexEryO2) and graphene oxide compound Er ions cerium oxide (GOCexEryO2) X-ray diffraction spectrogram。
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 as it is shown in figure 1, work as CexEryO2Exciting light induced electron after absorbing light energy, the carbon dioxide reduction discharged in sodium bicarbonate solution is methanol by light induced electron, CexEryO2The photohole stayed after absorbing light energy is absorbed by the sulfite ion in solution, is converted into sulfate ion。
In some embodiments providing a kind of composite photo-catalyst, described composite photo-catalyst includes the graphene oxide of stratiform and is distributed in the Ce of described surface of graphene oxidexEryO2Granule, wherein said CexEryO2The span of middle x is the span of 0 < x < 1, y is 0.01 < y < 1, and the energy gap of described composite photo-catalyst is 3.15-2.65eV。
Comparatively preferred, described graphene oxide content in described composite photo-catalyst is 0.0-4.0wt%。
Comparatively preferred, described CexEryO2Energy gap be 3.15-2.75eV。
Comparatively preferred, described CexEryO2Particle diameter be 3.4-4.8nm。
Comparatively preferred, the particle diameter of described composite photocatalyst material is 5-8nm。
The preparation method in some embodiments providing a kind of above-mentioned composite photo-catalyst includes: by solubility cerium salt, solubility erbium salt dissolves and alkaline solution mixes to and is precipitated as glassy yellow, obtain after mixed liquor mixes with graphene oxide suspension hydro-thermal reaction 8-6h at 160-180 DEG C, prepare described composite photo-catalyst。
Comparatively preferred, the mass percent of described solubility cerium salt, solubility erbium salt and graphene oxide is 1:0.062:0.040。
Comparatively preferred, described solubility cerium salt includes any one or two or more combination in cerous nitrate, cerium chloride or cerous sulfate, but is not limited to this。
Comparatively preferred, described solubility erbium salt includes any one or two or more combination in Erbium trinitrate, Erbium trichloride, but is not limited to this。
Comparatively preferred, described alkaline solution includes any one or two or more combination in sodium hydroxide solution, potassium hydroxide, but is not limited to this。
Comparatively preferred, the pH value of described graphene oxide suspension is more than 10。
Comparatively preferred, the pH value of described mixed solution is more than 10。
In some embodiments provide above-mentioned composite photocatalyst material in photocatalysis carbon dioxide be the application in methanol。
Below in conjunction with drawings and Examples, the technology of the present invention is further explained。
Embodiment 1
(1) prepared by graphene oxide: adopt the Hummers method improved to prepare graphene oxide (GO)。By 2.0g graphite (99.85%, Chinese Shanghai reagent head factory) put in 500ml beaker with 1.0g sodium nitrate, add 50ml concentrated sulphuric acid, under condition of ice bath, be slowly added to 6.0g potassium permanganate, stirring reaction 2h, continue stirring 2h after then heating to 35 DEG C, be then slowly added to the deionized water of 200ml, continuously stirred 20min, add the hydrogen peroxide of 20ml5%, neutralize unreacted potassium permanganate, after becoming glassy yellow to solution, continue at room temperature to stir 2h。Reaction system is staticly settled, pours out supernatant, lower sediment is filtered, wash at least 3 times with 5%HCl, then wash several times with 2000ml distilled water。Namely product dry 6h in 60 DEG C of vacuum drying ovens is obtained GO。As shown in Figure 2 a, can the two-dimensional sheet structure of graphene oxide visible in detail from figure。
(2)GOCexEryO2Preparation: weigh GO that quality is 0.0103g in 20ml deionized water, stir 2h, ultrasonic vibration 3h, obtain the GO suspension of stable homogeneous。Accurately weigh CeCl successively3·7H2O (0.5587g, 1.5mmol) and Er (NO3)3·5H2O (0.0160g, 0.036mmol) is dissolved in 20mL ultra-pure water and stirs to being completely dissolved, and is slowly added dropwise NaOH (1.0mol/L, 15mL) to pH > 10 in solution, continues stirring until mixed liquor is precipitated as glassy yellow, obtains solution A.
Being slowly added dropwise in solution A by GO suspension under magnetic stirring, stirring 1h makes its mix homogeneously more ultrasonic 3h。Finally this mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, it is placed in calorstat at 180 DEG C after hydro-thermal reaction 8h, products therefrom is centrifuged, washs three times, put into afterwards in vacuum drying oven and dry (60 DEG C, 6h), Er ions and graphene-supported cerium oxide hybrid material are obtained。As shown in Figure 2 a-2d, as can be seen from the figure CexEryO2Being distributed in surface of graphene oxide, sample particle diameter is about about 5nm, as it is shown on figure 3, at 595cm-1There is a small peak at place, and this peak is the O owing to trivalent cerium ion causes2-The secondary Raman vibration peak of defect, it was shown that containing Ce in obtained sample3+Impurity。19The catalysis helping to improve material of oxygen vacancy is active, and as shown in Figure 4, erbium doped and load GO all make CeO2Absorption band edge generation red shift, illustrate that erbium doped and load GO extend CeO2Response range to spectrum, it is expected to improve the utilization rate to visible ray。
(3) photo catalytic reduction CO2And the analysis of product: photo catalytic reduction CO2Reaction carries out in Photoreactor, utilizes 250WXe lamp as light source, and instrument is furnished with freeze cycle water system and ensures that temperature of reaction system is steady state value (25 ± 2 DEG C)；The Na of 0.1mol/L it is in concentration2SO3And NaHCO3Mixed liquor 250ml adds the catalyst of 0.1g, then in suspension, leads to CO2Bubbling 20min, to remove the oxygen being dissolved in solution。Illumination 5h, the solution in 1h abstraction reaction system, the centrifuging and taking supernatant, measure methanol yield。
The impact on methanol yield of the table 1 Er ions amount
The data of table 1 show, when erbium content is CeO2Quality 2.0% time, the productivity that photocatalytic reduction of carbon oxide is methanol is the highest。
The impact on methanol yield of the table 2 graphene oxide-loaded amount
As shown in Table 2, when the load capacity of GO is CexEryO2Catalyst quality 4.0% time, the productivity of methanol reaches maximum, equal to 66.9 μm of ol g-1cat.·h-1。
Embodiment 2
(1) prepared by graphene oxide: adopt the Hummers method improved to prepare graphene oxide (GO)。By 2.0g graphite (99.85%, Chinese Shanghai reagent head factory) put in 500ml beaker with 1.0g sodium nitrate, add 50ml concentrated sulphuric acid, under condition of ice bath, be slowly added to 6.0g potassium permanganate, stirring reaction 2h, continue stirring 2h after then heating to 35 DEG C, be then slowly added to the deionized water of 200ml, continuously stirred 20min, add the hydrogen peroxide of 20ml5%, neutralize unreacted potassium permanganate, after becoming glassy yellow to solution, continue at room temperature to stir 2h。Reaction system is staticly settled, pours out supernatant, lower sediment is filtered, wash at least 3 times with 5%HCl, then wash several times with 2000ml distilled water。Namely product dry 6h in 60 DEG C of vacuum drying ovens is obtained GO。
(2)GOCexEryO2Preparation: weigh GO that quality is 0.1000g in 20ml deionized water, stir 2h, ultrasonic vibration 3h, obtain the GO suspension of stable homogeneous。Accurately weigh CeCl successively3·7H2O (1.1170g, 3.0mmol) and Er (NO3)3·5H2O (0.0320g, 0.072mmol) is dissolved in 20mL ultra-pure water and stirs to being completely dissolved, and is slowly added dropwise NaOH (1.0mol/L, 15mL) to pH > 10 in solution, continues stirring until mixed liquor is precipitated as glassy yellow, obtains solution A.
Being slowly added dropwise in solution A by GO suspension under magnetic stirring, stirring 1h makes its mix homogeneously more ultrasonic 3h。Finally this mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, it is placed in calorstat rear, products therefrom is centrifuged, washs three times, put into afterwards in vacuum drying oven and dry (60 DEG C, 6h), Er ions and graphene-supported cerium oxide hybrid material are obtained。As it is shown in figure 5, figure observes the electron affinity energy of C1s, O1s and Ce3d respectively。As shown in Figure 6, according to Debye-Scherrer formula: D=k λ/(Wcos θ) can calculate the grain size CeO of hybrid material2Mean diameter be 3.4nm, the CeO of Er ions2Particle diameter be the Er ions CeO after 4.8nm and load graphene oxide2The particle diameter of hybrid material is 5.1nm, and the doping of this addition showing GO and erbium has promoted CeO2The growth of crystal。
(3) photo catalytic reduction CO2And the analysis of product: photo catalytic reduction CO2Reaction carries out in Photoreactor, utilizes 250WXe lamp as light source, and instrument is furnished with freeze cycle water system and ensures that temperature of reaction system is steady state value (25 ± 2 DEG C)；The Na of 0.1mol/L it is in concentration2SO3And NaHCO3Mixed liquor 250ml adds the catalyst of 0.1g, then in suspension, leads to CO2Bubbling 20min, to remove the oxygen being dissolved in solution。Illumination 5h, the solution in 1h abstraction reaction system, the centrifuging and taking supernatant, measure methanol yield。
Above detection means adopts Shimadzu 2450 type ultraviolet-uisible spectrophotometer to be used for measuring diffuse-reflectance spectrum；FEI Co. of U.S. TecnaiG22p type high resolution TEM is for observing pattern and the size of catalyst；X-ray diffractometer (BrukerD8) is for characterizing the crystal structure of catalyst；U.S.'s Agilent company 7890B type gas chromatograph is used for detecting photo catalytic reduction product；France's JY company LabRamHR800 type microscopic confocal Raman spectrometer is for characterizing the Raman displacement of catalyst；Shanghai is used for light-catalyzed reaction than bright Instrument Ltd. BL-GHX-V type photochemical reactor。
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. a composite photocatalyst material, it is characterised in that: described composite photo-catalyst includes the graphene oxide of stratiform and is distributed in the Ce of described surface of graphene oxidexEryO2Granule, wherein said CexEryO2The span of middle x is the span of 0 < x < 1, y is 0.01 < y < 1, and the energy gap of described composite photo-catalyst is 3.16-2.65eV。
2. composite photocatalyst material according to claim 1, it is characterised in that: described graphene oxide content in described composite photo-catalyst is 0.0-4.0wt%。
3. composite photocatalyst material according to claim 1, it is characterised in that: described CexEryO2Energy gap be 3.16-2.65eV。
4. composite photocatalyst material according to claim 1, it is characterised in that: described CexEryO2Particle diameter be 3.4-4.8nm,
And/or, the particle diameter of described composite photocatalyst material is 5-8nm。
5. the preparation method of the composite photocatalyst material described in any one of claim 1-4, it is characterized in that including: by solubility cerium salt, solubility erbium salt dissolves and alkaline solution mixes to and is precipitated as glassy yellow, obtain after mixed liquor mixes with graphene oxide suspension hydro-thermal reaction 8-6h at 160-180 DEG C, prepare described composite photo-catalyst。
6. the preparation method of composite photocatalyst material according to claim 5, it is characterised in that: the mass percent of described solubility cerium salt, solubility erbium salt and graphene oxide is 1:0.062:0.040。
7. the preparation method of composite photocatalyst material according to claim 5, it is characterised in that: described solubility cerium salt includes any one or two or more combination in cerous nitrate, cerium chloride or cerous sulfate,
And/or, described solubility erbium salt includes any one or two or more combination in Erbium trinitrate, Erbium trichloride,
And/or, described alkaline solution includes any one or two or more combination in sodium hydroxide solution, potassium hydroxide。
8. the preparation method of composite photocatalyst material according to claim 5, it is characterised in that: the pH value of described graphene oxide suspension is more than 10。
9. the preparation method of composite photocatalyst material according to claim 5, it is characterised in that: the pH value of described mixed solution is more than 10。
10. the composite photocatalyst material described in claim 1-9 in photocatalysis carbon dioxide be the application in methanol。
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