CN108940308A - A kind of preparation of platinum cobalt composition metal photo-thermal catalyst and its application in methane carbon dioxide reformation - Google Patents
A kind of preparation of platinum cobalt composition metal photo-thermal catalyst and its application in methane carbon dioxide reformation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims description 26
- 239000002184 metal Substances 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 title claims description 16
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 title claims description 9
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 title description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 33
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000002407 reforming Methods 0.000 claims abstract description 7
- 238000009938 salting Methods 0.000 claims abstract description 7
- 239000007769 metal material Substances 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 63
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 16
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 229960004424 carbon dioxide Drugs 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000002153 concerted effect Effects 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUVYWBZETQFDHA-UHFFFAOYSA-N [Co]=O.[O-2].[Al+3].[O-2].[O-2].[Al+3] Chemical compound [Co]=O.[O-2].[Al+3].[O-2].[O-2].[Al+3] XUVYWBZETQFDHA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 238000010792 warming 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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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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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of photo-thermal catalyst of methane and carbon dioxide preparing synthetic gas by reforming and its applications.Oxidation cobalt nano-particle is prepared first, is loaded on the alumina support, then by obtained oxidation cobalt nano-particle and alumina composite metal material CoO NPs-Al2O3The middle salting liquid that platiniferous is added and stirring are dried later, calcining obtains Pt/CoO-Al2O3Composite optothermal material.Under light irradiation, which has very high photo-thermal catalytic conversion efficiency to methane and carbon dioxide；The success of the catalyst is prepared as methane and CO2Efficient, the green conversion of gaseous mixture in a mild condition provides good opportunity.
Description
Technical field
The present invention relates to a kind of photo-thermal catalyst of methane and carbon dioxide preparing synthetic gas by reforming, and in particular to a kind of platinum is received
The preparation of the composition metal photo-thermal catalyst of rice grain-oxidation cobalt nano-particle on the alumina support, belongs to Binary plasma
Resonance light heat coupling material preparation field.
Background technique
With the getting worse of the environmental problems such as global warming, people are to greenhouse gases CO2And CH4It handles and utilizes
Degree of concern is also higher and higher.Effective reformation of two kinds of greenhouse gases is not only by CO2It is used as feedstock circulation, and because of reaction
Using light source as sole energy source, it can be used for effective conversion of the luminous energy to chemical energy.Solar energy uses it with inexhaustible
Inexhaustible feature.Driven by Solar Energy CH is utilized if can be realized4And CO2Reforming process can not only realize the complete of synthesis gas production
Full greenization, and have the potentiality of trapping and fixed solar energy.
Nineteen twenty-eight, Fischer and Tropsch grind various metals catalytic methane and CO 2 reforming reaction
Study carefully.Hereafter numerous studies prove, VIII group transition metal has a catalytic activity to the reaction, noble metal (Pt, Pd, Ph, Ru,
Ir) catalyst catalytic activity with higher and carbon accumulation resisting ability, wherein Pt is considered as best composition.
Methane reforming with carbon dioxide activity is by the property of carried metal, carrier and metal, carrier on catalyst
And Support-metal strong interaction etc. influences, compared with other transition metal, platinum has higher in methane reaction kinetic
Reactivity and non-easy in inactivation.Although carrier function viewpoint is unified not yet, thermal stability is good, large specific surface area is high temperature
The precondition of reforming reaction catalyst choice carrier, and micropore and mesopore molecular sieve have unique cellular structure, it is also universal
With high stability and bigger serface.In addition, when carrier and metal are there are when strong interaction, it is greatly improved catalyst
Reactivity and anti-caking power.Therefore, we choose the carrier loaded high activity metal species of Large ratio surface, high thermal stability
Platinum prepares efficiency light thermocatalytic reforming reaction catalyst as research object.
Due to realizing that the activation of inertia c h bond all suffers from huge choose on thermodynamics and kinetics by photocatalysis means
War.Creating the concerted catalysis process under the conditions of light field and thermal field simultaneously using sunlight as sole energy source is a kind of effectively to push
The new paragon of C-H activation, compensates for the deficiency of single photocatalysis technology.Based on this, the present invention establishes Pt-Co-Al2O3It is polynary
Alloy enhances surface plasma resonance catalyst system.
Summary of the invention
That the purpose of the present invention is to provide a kind of methane and carbon dioxide preparing synthetic gas by reforming photo-thermal catalytic reforming activity is good,
The preparation method of the photo-thermal catalyst of the features such as simple production process, to probe into the catalyst under relatively mild conditions
Realize that methane and carbon dioxide photo-thermal is reformed.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of cobalt oxide-aluminium oxide photo-thermal catalyst preparation of platinum load the following steps are included:
(1) preparation of cobalt nano-particle is aoxidized:
The cobalt nitrate solution of 1 mM is prepared, the cobalt nitrate aqueous solution of 60-80 mL is measured and the mixing of 50 mL ethanol solutions is added
10 min are stirred, the lauryl amine solution that 1-5 mL is added stirs 5 min, and the hexane solution that 50 mL are added stirs 2 min, stops
Stirring stands 5min, takes upper solution in beaker, 30 min are stirred in 50 DEG C of water-bath.Stand 12 h.
(2) cobalt nano-particle-alumina composite metal material (CoO NPs-Al is aoxidized2O3) preparation:
0.5-3 g alumina powder is added in the solution of above-mentioned steps (1), after stirring 2 h at room temperature, centrifugation, is done washing
Dry, calcining obtains the composite material of CoO NPs load on alumina.
(3) cobalt nano-particle-alumina composite material (CoO NPs-Al is aoxidized2O3) on supported platinum nano particle (Pt
NPs preparation):
By the obtained oxidation cobalt nano-particle of step (2) and alumina composite metal material (CoO NPs-Al2O3) in be added 10-
The salting liquid of 90 mL platiniferous simultaneously stirs 12 h, and the quality of institute's platiniferous is 1 mg/mL in the salting liquid of platinum, is dried, is forged later
Burning obtains Pt/CoO-Al2O3Compound optothermal material.
Mixing speed in step (2) is 5000 r/min, and calcination temperature is 200 DEG C -300 DEG C.
Calcination temperature in step (3) is 300 DEG C -700 DEG C, and platinum content is 0.5-3 wt%.
A kind of application of the photo-thermal catalyst as described above for methane carbon dioxide reformation: compound photo-thermal catalyst
Preparing synthetic gas by reforming production CO reaches 6400 μm of ol.g under simulated solar irradiation-1.s-1, produce H2Reach 7000 μm of ol.g-1.s-1。
Specific step is as follows for photo-thermal catalytic methane CO 2 reformation preparing synthetic gas:
(1) Pt/CoO- by screening mesh number for 60-80 mesh is packed into the rectangular quartz reactor of the 3*3*0.2 cm of customization
Al2O3Composition metal photo-thermal catalyst is irradiated in light, and the CH that molar content is 1:1 is passed through under normal pressure4:CO2Gas.
(2) the thermocatalytic product of light is analyzed with gas-chromatography, is quantified by retention time and peak area.
Remarkable advantage of the invention is:
(1) catalyst preparation is simple, using solar energy as unique driving force, while realizing two kinds of greenhouse gas methanes and two
The reformation of carbonoxide avoids conventional high-temperature, the condition of high pressure, realizes the weight of methane and carbon dioxide under mild conditions
It is whole, be conducive to the sustainable development and utilization of environment and the energy.
(2) Pt/CoO-Al2O3The catalytic activity height of composition metal photo-thermal catalyst, good cycle, simple production process,
It can macroscopic view preparation, easily recycling.
Detailed description of the invention
Fig. 1 is Pt/CoO-Al2O3、Pt/Al2O3、CoO-Al2O3、Al2O3DRS figure；
Fig. 2 is Pt/CoO-Al2O3XRD diagram；
Fig. 3 is Pt/CoO-Al2O3Production CO activity figure；
Fig. 4 is Pt/CoO-Al2O3Production H2Activity figure.
Specific embodiment
Embodiment is set forth below and further illustrates the present invention.
Embodiment 1
1. the preparation of catalyst:
(1) preparation of cobalt load on alumina:
100 mL cobalt nitrate aqueous solutions and 50 mL ethanol solutions are mixed 10 min, added by the cobalt nitrate solution for preparing 1 mM
The lauryl amine solution for entering 1 mL stirs 5 min, and the hexane solution that 50 mL are added stirs 2 min, stops stirring and stands 5 min, takes
Upper solution stirs 30 min in beaker in 50 DEG C of water-bath.Stand 12 h.
(2) cobalt nano-particle-alumina composite metal material (CoO NPs-Al is aoxidized2O3) preparation:
The alumina powder of 1 g is added in the solution of above-mentioned steps (1), is 5000 with revolving speed after stirring 2 h at room temperature
R/min centrifugation, washing, dry, calcining obtain the composite material of CoO NPs load on alumina.
(3) cobalt nano-particle-alumina composite material (CoO NPs-Al is aoxidized2O3) on supported platinum nano particle (Pt
NPs preparation):
Take the obtained oxidation cobalt nano-particle of step (2) and alumina composite material (CoO NPs-Al2O3) 0.5 g is added to and contains
12 h are stirred in the salting liquid of platinum, the mass concentration of platinum is 1 mg/mL in the salting liquid of platinum, and 2.5 ml of additional amount is carried out later
Drying calcines 4 h at 300 DEG C and obtains Pt/CoO-Al2O3Compound optothermal material.
2. active testing:
(1) Pt/CoO- by screening mesh number for 60-80 mesh is packed into the rectangular quartz reactor of the 3*3*0.2 cm of customization
Al2O3Composition metal photo-thermal catalyst is irradiated in light, and the CH that content molal weight is 1:1 is passed through under normal pressure4:CO2Gas.
(2) the thermocatalytic product of light is analyzed with Agilent gas-chromatography, is carried out by retention time and peak area
It is quantitative.
Embodiment 2
Specific Pt/CoO-Al2O3Preparation method and this part embodiment 1 are essentially identical, the difference is that containing metal platinum
Amount is changed to 1.0 wt %, and calcination temperature is 300 DEG C.
Embodiment 3
Specific Pt/CoO-Al2O3Preparation method and this part embodiment 1 are essentially identical, the difference is that containing metal platinum
Amount is changed to 1.5 wt%, and calcination temperature is 400 DEG C.
Embodiment 4
Specific Pt/CoO-Al2O3Preparation method and this part embodiment 1 are essentially identical, the difference is that containing metal platinum
Amount is changed to 2.0 wt%, and calcination temperature is 500 DEG C.
Embodiment 5
Specific Pt/CoO-Al2O3Preparation method and this part embodiment 1 are essentially identical, the difference is that containing metal platinum
Amount is changed to 2.5 wt%, and calcination temperature is 600 DEG C.
Embodiment 6
Specific Pt/CoO-Al2O3Preparation method and this part embodiment 1 are essentially identical, the difference is that containing metal platinum
Amount is changed to 3.0 wt%, and calcination temperature is 700 DEG C.
From the UV-Vis-NIR characterization result (Fig. 1) of catalyst it can be seen that carrier (Al2O3) in 400-1200 nm ranges
It is interior almost without light absorption, Co/Al2O3Catalyst has certain light absorption within the scope of 400-1200 nm.Pt-Co/Al2O3
And Pt/Al2O3There is a small peak packet there are apparent light absorption in 400-1200 nm and in 400-450 nm in catalyst, this
It is characteristic absorption caused by Pt metal oneself excitation；
Due to Pt-Co/Al2O3The content of noble metal and cobalt metal ion is considerably less in catalyst, when activity component load quantity is low
When carrier Monolayer Dispersion threshold values, the result of the XRD characterization of Fig. 2 will not detect the characteristic diffraction peak of (Pt, Co) component.This
Also illustrate that active component can be in Al2O3It is evenly dispersed in substrate；
As can be seen from Figure 3, Pt-Co/Al2O3Its photo-thermal of catalyst is catalyzed CH4And CO2The yield of preparing synthetic gas CO is apparently higher than merely
Thermocatalytic, photo-thermal concerted catalysis is 386o C yield, thermocatalytic will be 500o C can be only achieved；
As can be seen from Figure 4, Pt-Co/Al2O3Its photo-thermal of catalyst is catalyzed CH4And CO2The yield of preparing synthetic gas CO is apparently higher than merely
Thermocatalytic, photo-thermal concerted catalysis is 386o C yield is much larger than thermocatalytic 500o Yield when C；
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Claims (7)
1. a kind of platinum cobalt composition metal photo-thermal catalyst, it is characterised in that: Pt nanoparticle Pt NPs and oxidation cobalt nano-particle
CoO NPs is supported on aluminium oxide Al2O3Upper composition, it is 0.5%-3% that wherein the quality of Pt NPs, which accounts for entire composite catalyzing agent content,；
The mass fraction that CoO NPs accounts for entire composite catalyst is 0.6%-0.8%.
2. a kind of prepare a kind of method of platinum cobalt composition metal photo-thermal catalyst as described in claim 1, it is characterised in that: packet
Include following steps:
(1) preparation of cobalt nano-particle is aoxidized:
Cobalt nitrate solution is prepared, the cobalt nitrate aqueous solution of 60-80 mL is measured and the mixing of 50mL ethanol solution is added
10min, the lauryl amine solution that 1-5 mL is added stir 5min, and the hexane solution that 50mL is added stirs 2 min, stop stirring and stand
5min takes upper solution in beaker, stirs 30min in 50 DEG C of water-bath.Stand 12 h；
(2) cobalt nano-particle-alumina composite metal material CoO NPs-Al is aoxidized2O3Preparation:
0.5-3 g alumina powder is added in the solution of above-mentioned steps (1), after stirring 2 h at room temperature, centrifugation, is done washing
Dry, calcining obtains the composite material of CoO NPs load on alumina；
(3) cobalt nano-particle-alumina composite material CoO NPs-Al is aoxidized2O3The preparation of upper supported platinum nano particle Pt NPs:
By the obtained oxidation cobalt nano-particle of step (2) and alumina composite metal material CoO NPs-Al2O3Middle addition 10-90
The salting liquid of mL platiniferous simultaneously stirs 12 h, and the quality of institute's platiniferous is 1 mg/mL in the salting liquid of platinum, is dried, is calcined later
Obtain Pt/CoO-Al2O3Compound optothermal material.
3. the preparation method of platinum cobalt composition metal photo-thermal catalyst according to claim 2, it is characterised in that: step (1)
In, the concentration of cobalt nitrate solution is 1 mM.
4. the preparation method of platinum cobalt composition metal photo-thermal catalyst according to claim 2, it is characterised in that: step (2)
In, the calcination temperature is 200 DEG C -300 DEG C, and calcination time is 2-3 h.
5. the preparation method of platinum cobalt composition metal photo-thermal catalyst according to claim 2, it is characterised in that: step (3)
In, the calcination temperature is 300 DEG C -700 DEG C, and calcination time is 4-5 h.
6. a kind of application of platinum cobalt composition metal photo-thermal catalyst as described in claim 1, it is characterised in that: for methane and
In the reaction of CO 2 reformation preparing synthetic gas.
7. the application of platinum cobalt composition metal photo-thermal catalyst according to claim 6, it is characterised in that: composition metal photo-thermal
The catalyst yield that preparing synthetic gas by reforming produces CO under light irradiation reaches 6400 μm of ol.g-1.s-1, produce H2Yield reaches 7000 μ
mol.g-1.s-1。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810788023.1A CN108940308B (en) | 2018-07-18 | 2018-07-18 | Preparation of platinum-cobalt composite metal photo-thermal catalyst and application of platinum-cobalt composite metal photo-thermal catalyst in methane carbon dioxide reforming |
Applications Claiming Priority (1)
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