CN115254138B - Preparation method and application of Ir-CoO/alumina photo-thermal catalyst - Google Patents
Preparation method and application of Ir-CoO/alumina photo-thermal catalyst Download PDFInfo
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- CN115254138B CN115254138B CN202210987565.8A CN202210987565A CN115254138B CN 115254138 B CN115254138 B CN 115254138B CN 202210987565 A CN202210987565 A CN 202210987565A CN 115254138 B CN115254138 B CN 115254138B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title description 2
- 239000002105 nanoparticle Substances 0.000 claims abstract description 53
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 229910002515 CoAl Inorganic materials 0.000 claims description 44
- 239000003245 coal Substances 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- KZLHPYLCKHJIMM-UHFFFAOYSA-K iridium(3+);triacetate Chemical compound [Ir+3].CC([O-])=O.CC([O-])=O.CC([O-])=O KZLHPYLCKHJIMM-UHFFFAOYSA-K 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229920003081 Povidone K 30 Polymers 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 150000002503 iridium Chemical class 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 239000000203 mixture Substances 0.000 claims 1
- 230000005684 electric field Effects 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 3
- 229960001545 hydrotalcite Drugs 0.000 abstract description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 16
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 11
- 238000010335 hydrothermal treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to photo-thermal coupling catalytic CO 2 The technical field of hydrogenation, in particular to Ir nanoparticle loaded hydrotalcite derived Ir-CoO/Al 2 O 3 A photo-thermal catalyst, a preparation method and application thereof. Ir nano particles in the catalyst are dispersed on the surface of CoO generated in situ, al 2 O 3 The aggregation of Ir-CoO active centers is effectively inhibited as a carrier. The Ir-CoO interface is induced to generate a strong local electric field under the illumination, so that the generation and transfer of carriers are accelerated, and the activation of reactants is promoted; meanwhile, under a strong local electric field, ir-CoO shows a synergistic enhanced photo-thermal effect, so that the temperature around an active site is quickly increased, and the reaction kinetics is improved. Thus, the catalyst exhibits excellent photo-thermal coupling catalytic CO 2 Hydrogenation performance. Meanwhile, the noble metal content in the catalyst is low, so that the cost of the catalyst is greatly reduced, and the catalyst has good practical application value.
Description
Technical Field
The photo-thermal coupling catalysis of CO 2 The technical field of hydrogenation, in particular to an Ir-CoO/Al derived from Ir nanoparticle-loaded hydrotalcite 2 O 3 A preparation method and application of a photo-thermal catalyst.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
In the prior art, photo-thermal coupling catalyzes CO 2 Hydrogenation can be carried out under mild reaction conditions to convert CO 2 Is converted into chemicals with high added value, and is an effective way for relieving environmental pollution and energy crisis. In a plurality of COs 2 In the hydrogenation product, CH 4 As a fuel with higher heat value, the natural gas is the main component and has been widely applied to the field of energy-intensive application, thus CO 2 Hydrogenation for preparing CH 4 Has important significance.
The noble metal nanoparticle supported metal oxide composite is CO 2 A mainstream catalyst in hydrogenation reactions. The noble metal nano-particles can be used as active sites, and the carrier material disperses the active sites, so that aggregation of the nano-particles is reduced, and the catalyst is more stable. However, conventional metal oxide supports have a low solar light absorption capacity, resulting in a low catalytic activity. Thus, CO was developed with a broad solar absorption range and high catalytic activity 2 The hydrogenation catalyst has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides Ir nanoparticle-supported hydrotalcite derived Ir-CoO/Al 2 O 3 A preparation method and application of a photo-thermal catalyst. The catalyst has excellent light absorption capacity and can effectively utilize sunlight. Under illumination, the Ir-CoO interface can induce a strong local electric field to promote the generation and transfer of carriers; in addition, the strong interaction of Ir and CoO enhances the photo-thermal effect at the interface, effectively increases the local temperature of the active site, and further promotes the activation of the reactants. High stability Al 2 O 3 The nano-sheet can effectively inhibit aggregation of Ir-CoO active centers and improve the stability of the catalyst. Therefore, the catalyst exhibits high catalytic activity and excellent stability.
Specifically, the technical scheme of the invention is as follows:
in a first aspect of the invention, there is provided an Ir-CoO/Al 2 O 3 Photo-thermal catalyst, the Ir-CoO/Al 2 O 3 The photo-thermal catalyst comprises Ir nano-particles, coO and Al 2 O 3 The carrier, ir nano particles are dispersed on the surface of the in-situ generated CoO, and then the Ir-CoO is inlaid in Al 2 O 3 A carrier; the photo-thermal catalyst is a porous material with three-dimensional lamellar.
In a second aspect of the present invention, there is provided the above Ir-CoO/Al 2 O 3 The preparation method of the photo-thermal catalyst adopts an impregnation method, firstly Ir nano particles are loaded on cobalt-aluminum hydrotalciteSurface (Ir/CoAl LDH), then calcining the Ir/CoAl LDH in a hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 A composite material.
In a third aspect of the invention, there is provided an Ir-CoO/Al 2 O 3 Photo-thermal catalyst and Ir-CoO/Al 2 O 3 Photo-thermal catalyst obtained by preparation method of photo-thermal catalyst catalyzes CO under photo-thermal condition 2 Application in hydrogenation.
One or more of the technical schemes in the invention has the following beneficial effects:
(1) The photo-thermal coupling catalytic CO adopted by the invention 2 Hydrogenation technology can make CO 2 Conversion to CH at lower temperatures (100-250 ℃ C.) and atmospheric pressure 4 The problems of excessive energy consumption and safety caused by high temperature and high pressure in the traditional thermocatalytic reaction are greatly avoided.
(2) Ir-CoO/Al supported on 0.16wt.% Ir nanoparticles 2 O 3 The catalyst showed excellent CH at 250℃and under light 4 The rate of production was 128.9mmol g cat -1 h -1 Selectivity is 92%, CO 2 The conversion was 65.5%.
(3) The CoAl LDH is easy to prepare, has stable property and is beneficial to mass production and preservation; ir nano particles are loaded on the CoAl LDH by an impregnation method, so that the method is simple and the operation is easy.
(4) In situ conversion of Ir/CoAl LDH to Ir-CoO/Al by calcination 2 O 3 Under the action of a plasma electric field, the Ir-CoO interface can accelerate the generation and transfer of carriers and promote the activation of reactants; in addition, the process of attenuation of local electromagnetic field enhancement also leads to a sharp increase in temperature at the interface, and the generated heat can be transferred to the Ir nanoparticles due to their higher thermal conductivity. Thus, coO can act as a "nano-heater" to rapidly increase the temperature around the active site, increasing the kinetics of the reaction.
(5) High stability Al 2 O 3 The nano-sheet can effectively inhibit aggregation of Ir-CoO active centers, thereby ensuring long service life of the composite catalyst.
(6) The catalyst has the advantages of low noble metal content, low cost, mild reaction conditions, convenient operation, energy conservation, no generation of redundant harmful substances in the production process, environmental protection and contribution to realizing industrial production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application.
FIG. 1 is Ir-CoO/Al prepared in example 1 2 O 3 TEM and HRTEM images of (a).
FIG. 2 is a graph of Ir/CoAl LDH and Ir-CoO/Al prepared in example 1 2 O 3 Is a XRD pattern of (C).
FIG. 3 is Ir-CoO/Al of different Ir nanoparticle loading levels prepared in example 1, example 2, example 3 and example 4 2 O 3 Catalyst and CoO/Al prepared in comparative examples 1 and 2 2 O 3 And Ir/Al 2 O 3 Catalyst photo-thermal catalysis of CO 2 Hydrogenation CH 4 A rate profile is generated as a function of reaction temperature.
FIG. 4 is a 0.16% Ir-CoO/Al solution prepared in example 1 2 O 3 Catalyst photo-thermal catalysis of CO 2 CH in hydrogenation reaction process 4 Selectivity and CO 2 Conversion varies with temperature.
FIG. 5 is a 0.16% Ir-CoO/Al solution prepared in example 1 2 O 3 Thermal catalysis of catalysts and photo-thermal catalysis of CO 2 Hydrogenation performance comparison.
FIG. 6 is a 0.16% Ir-CoO/Al preparation of example 1 2 O 3 Stability test of the catalyst.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As previously described, CO is now 2 The hydrogenation has the problems of higher temperature and pressure required by the reaction and lower conversion rate and selectivity, and in order to solve the problems, the invention provides an Ir-CoO/Al catalyst 2 O 3 A photo-thermal catalyst, a preparation method and application thereof.
In one embodiment of the invention, an Ir-CoO/Al 2 O 3 Photo-thermal catalyst, the Ir-CoO/Al 2 O 3 The photo-thermal catalyst comprises Ir nano-particles, coO and Al 2 O 3 The carrier, ir nano particles are dispersed on the surface of CoO generated in situ, ir-CoO is inlaid in Al 2 O 3 On the nanoplatelets.
Ir-CoO/Al 2 O 3 The catalyst has a wider visible light absorption range, can induce a strong local electric field to accelerate the generation and transfer of carriers, and further promotes the activation of reactants. In addition, due to the enhancement of the local electric field, the Ir-CoO shows a synergistic enhanced photo-thermal effect, so that the CoO can be used as a photodynamic 'nano heater' to improve the local temperature of the Ir active site, and greatly promote the catalytic reaction.
Further, based on the mass of the catalyst being 100%, the Ir nanoparticle load obtained by an inductively coupled plasma emission spectrometry test is 0.03% -0.23%, wherein the optimal Ir nanoparticle load is 0.16%. The noble metal content in the catalyst is low, so that the cost can be greatly reduced. In addition, the content of the metal nano particles is controlled, so that the uniform distribution of the metal particles on the carrier is improved, and on the other hand, rich adsorption sites are provided for reactants, and the catalytic activity is improved.
In one embodiment of the present invention, al 2 O 3 The size of the nano-sheet is 2-3um, the size of the Ir nano-particle is 1-2.5nm, and the size of CoO is 5-20nm.
In one embodiment of the invention, an Ir-CoO/Al 2 O 3 The preparation method of the photo-thermal catalyst comprises the steps of firstly adopting a hydrothermal method to synthesize CoAl LDH and Ir nano particles respectively, adopting an impregnation method to load the Ir nano particles on the surface of the CoAl LDH, and finally calcining in a hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 . In the conventional preparation method, metal oxide is prepared firstly, and then metal nano-is loaded on the surface of the metal oxide by an impregnation method. However, the in-situ growth method can improve the interaction between the metal nano particles and the metal oxide, slow down or even avoid the sintering and deactivation of the metal nano particles in the reaction, and improve the stability of the catalyst.
In one embodiment of the present invention, there is provided a method for preparing the above-described CoAl LDH, comprising: cobalt salt, aluminum salt, organic compound and organic solvent are uniformly mixed, and the CoAl LDH is synthesized by a solvothermal method.
In one embodiment of the invention, the cobalt salt, aluminum salt, organic compound and organic solvent are used in amounts of 1.8-9mmol, 0.9-4.5mmol, 1.2-6mmol, 5-25mmol and 15-80mL, respectively.
In one embodiment of the present invention, there is provided a method for preparing the above Ir nanoparticle, comprising: ir nano particles are synthesized by a solvothermal method by uniformly mixing iridium salt, a surfactant and an organic solvent.
In one embodiment of the invention, the iridium salt, surfactant and organic solvent are used in amounts of 0.01-0.05mmol, 50-200mg and 10-40mL, respectively.
In one embodiment of the invention, the cobalt salt is cobalt nitrate, the aluminum salt is aluminum nitrate, the organic compound is urea and ammonium fluoride, and the organic solvent is methanol.
In one embodiment of the present invention, the iridium salt is one or more of iridium chloride, iridium acetate and chloroiridic acid, the surfactant is polyvinylpyrrolidone (PVP), and the organic solvent is ethylene glycol.
In one embodiment of the invention, the solvothermal method is carried out at a temperature of 130-160 ℃ for a reaction time of 10-18h.
In one embodiment of the invention, the temperature of the solvothermal method for preparing the Ir nano particles is 170-210 ℃ and the reaction time is 18-24h.
In one embodiment of the invention, the specific process of loading Ir nanoparticles onto the surface of the CoAl LDH by impregnation is: dissolving the dried CoAl LDH into ethanol solution, adding Ir nanoparticle suspension, stirring at room temperature, and finally centrifugally drying to obtain the Ir/CoAl LDH.
In one embodiment of the invention, the dosage ratio of the CoAl LDH and Ir nano particles is 100:0.01 to 100:0.5.
in one embodiment of the invention, the calcination temperature is 300-500 ℃ and the reaction time is 1-3h.
In one embodiment of the invention, an Ir-CoO/Al 2 O 3 Photo-thermal catalyst and/or photo-thermal catalyst obtained by preparation method catalyze CO under photo-thermal condition 2 Application in hydrogenation.
Further, the catalytic conditions are: the light source is a xenon lamp with the wavelength of 420-780nm, the working current of 20A and the light intensity of 2W cm -2 ，CO 2 The flow rate is 4mL/min, H 2 The flow rate is 16mL/min, the reaction temperature is 100-250 ℃, and the reaction device is a gas-phase flow reactor.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
(1) 7.2mmol of cobalt nitrate, 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain CoAl LDH, and then centrifugally washing the product and drying at 70 ℃;
(3) 0.02mmol of iridium acetate and 100mg of PVP K30 are added into 15mL of ethylene glycol and stirred until dissolved;
(4) Transferring the mixed solution in the step (3) into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours to obtain an Ir nanoparticle solution;
(5) 200mg of dried CoAl LDH is weighed and dissolved in ethanol solution, then 1mL of Ir nanoparticle suspension is added, the mixed solution is continuously stirred for 6 hours at room temperature, and finally the Ir/CoAl LDH is obtained through centrifugal drying.
(6) Placing the prepared Ir/CoAl LDHCalcining in a muffle furnace at 450 ℃ for 2h under hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 A catalyst.
FIG. 1 is Ir-CoO/Al prepared in example 1 2 O 3 TEM and HRTEM images of (a). From TEM images, it can be seen that Ir nanoparticles are dispersed on the CoO surface instead of Al 2 O 3 A carrier; in the HRTEM image, lattice fringes with interplanar spacings of 0.22 and 0.24nm correspond to the (111) crystal planes of Ir nanoparticles and CoO, respectively. FIG. 2 is a graph of Ir/CoAl LDH and Ir-CoO/Al prepared in example 1 2 O 3 Is a XRD pattern of (C). It can be seen from the figure that upon calcination in a reducing atmosphere, the CoAl LDH undergoes a structural topological transformation into a cubic phase of CoO and amorphous Al 2 O 3 。
FIG. 4 is a 0.16% Ir-CoO/Al solution prepared in example 1 2 O 3 Catalyst photo-thermal catalysis of CO 2 CH in hydrogenation reaction process 4 Selectivity and CO 2 Conversion varies with temperature. As can be seen from the figure, CH with increasing reaction temperature 4 Selectivity and CO 2 The conversion also increased, showing the highest CH at 250 ℃ 4 Selectivity is 92%, corresponding to CO 2 The conversion was 65.5%.
FIG. 5 is a 0.16% Ir-CoO/Al solution prepared in example 1 2 O 3 Thermal catalysis of catalysts and photo-thermal catalysis of CO 2 Hydrogenation performance comparison. As can be seen from the figure, CH under photothermal conditions 4 The rate of formation is almost 6.8 times that under purely thermal conditions, indicating that illumination can significantly enhance the thermocatalytic reaction.
FIG. 6 is a 0.16% Ir-CoO/Al preparation of example 1 2 O 3 Stability test of the catalyst. As can be seen from the figure, CH in the reaction lasting 30 hours 4 Does not significantly decrease the yield of Ir-CoO/Al, indicating 2 O 3 The catalyst is highly stable.
Example 2
(1) 7.2mmol of cobalt nitrate, 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain CoAl LDH, and then centrifugally washing the product and drying at 70 ℃;
(3) 0.02mmol of iridium acetate and 100mg of PVP K30 are added into 15mL of ethylene glycol and stirred until dissolved;
(4) Transferring the mixed solution in the step (3) into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours to obtain an Ir nanoparticle solution;
(5) 200mg of dried CoAl LDH is weighed and dissolved in ethanol solution, then 2mL of Ir nanoparticle suspension is added, the mixed solution is continuously stirred for 6 hours at room temperature, and finally the Ir/CoAl LDH is obtained through centrifugal drying.
(6) Placing the prepared Ir/CoAl LDH in a muffle furnace, and calcining for 2h at 450 ℃ in a hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 A catalyst.
Example 3
(1) 7.2mmol of cobalt nitrate, 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain CoAl LDH, and then centrifugally washing the product and drying at 70 ℃;
(3) 0.02mmol of iridium acetate and 100mg of PVP K30 are added into 15mL of ethylene glycol and stirred until dissolved;
(4) Transferring the mixed solution in the step (3) into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours to obtain an Ir nanoparticle solution;
(5) 200mg of the dried CoAl LDH is weighed and dissolved in ethanol solution, then 0.5mL of Ir nanoparticle suspension is added, the mixed solution is continuously stirred for 6 hours at room temperature, and finally the Ir/CoAl LDH is obtained through centrifugal drying.
(6) Placing the prepared Ir/CoAl LDH in a muffle furnace, and calcining for 2h at 450 ℃ in a hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 A catalyst.
Example 4
(1) 7.2mmol of cobalt nitrate, 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain CoAl LDH, and then centrifugally washing the product and drying at 70 ℃;
(3) 0.02mmol of iridium acetate and 100mg of PVP K30 are added into 15mL of ethylene glycol and stirred until dissolved;
(4) Transferring the mixed solution in the step (3) into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours to obtain an Ir nanoparticle solution;
(5) 200mg of the dried CoAl LDH is weighed and dissolved in ethanol solution, then 0.25mL of Ir nanoparticle suspension is added, the mixed solution is continuously stirred for 6 hours at room temperature, and finally the Ir/CoAl LDH is obtained through centrifugal drying.
(6) Placing the prepared Ir/CoAl LDH in a muffle furnace, and calcining for 2h at 450 ℃ in a hydrogen atmosphere to obtain Ir-CoO/Al 2 O 3 A catalyst.
Comparative example 1
(1) 7.2mmol of cobalt nitrate, 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain CoAl LDH, and then centrifugally washing the product and drying at 70 ℃;
(3) Placing the prepared CoAl LDH in a muffle furnace, and calcining at 450 ℃ for 2h under a hydrogen atmosphere to obtain CoO/Al 2 O 3 A catalyst.
Comparative example 2
(1) 3.6mmol of aluminum nitrate, 4.8mmol of ammonium fluoride and 20mmol of urea are added into 50mL of methanol solution and stirred until dissolved;
(2) Transferring the mixed solution in the step (1) into a reaction kettle, and carrying out hydrothermal treatment at 150 ℃ for 12 hours to obtain Al (OH) 3 Centrifugally washing the precursor, and drying at 70 ℃;
(3) 0.02mmol of iridium acetate and 100mg of PVP K30 are added into 15mL of ethylene glycol and stirred until dissolved;
(4) Transferring the mixed solution in the step (3) into a reaction kettle, and carrying out hydrothermal treatment at 200 ℃ for 24 hours to obtain an Ir nanoparticle solution;
(5) 200mg of dried Al (OH) was weighed 3 Dissolving in ethanol solution, and adding 1mL of Ir nanoparticle suspension, stirring the mixed solution at room temperature for 6 hours, and finally obtaining Ir/Al (OH) through centrifugal drying 3 。
(6) Ir/Al (OH) to be prepared 3 Placing in a muffle furnace, calcining at 450 ℃ for 2h in a hydrogen atmosphere to obtain Ir/Al 2 O 3 A catalyst.
FIG. 3 is Ir-CoO/Al of different Ir nanoparticle loading levels prepared in example 1, example 2, example 3 and example 4 2 O 3 Catalyst and CoO/Al prepared in comparative examples 1 and 2 2 O 3 And Ir/Al 2 O 3 Catalyst photo-thermal catalysis of CO 2 Hydrogenation CH 4 A rate profile is generated as a function of reaction temperature. From the figure, it can be seen that CoO/Al prepared in comparative example 1 and comparative example 2 2 O 3 And Ir/Al 2 O 3 The catalyst showed very low CH 4 The production rate of Ir-CoO/Al prepared in examples 1-4 2 O 3 CH of catalyst 4 The production rate of the catalyst is greatly improved, which indicates that the synergistic effect of Ir and CoO can obviously improve the catalytic activity. In addition, 0.16% Ir-CoO/Al prepared in example 1 2 O 3 The catalyst shows the best catalytic performance, CH at 250 ℃ and under illumination 4 The production rate of (C) is as high as 128.9mmol g cat -1 h -1 。
Photo-thermal catalysis of CO 2 Hydrogenation test:
CO 2 the hydrogenation experiment is carried out in a photo-thermal catalytic micro-reaction system, and the reaction system is a flowing system. The catalytic conditions are as follows: the light source is a xenon lamp with the wavelength of 420-780nm, the working current of 20A and the light intensity of 2W cm -2 ，CO 2 The flow rate is 4mL/min, H 2 The flow rate is 16mL/min, and the reaction temperature is 100-250 ℃. Mixing catalyst 50mg with quartz sand 1.2g, placing into transparent quartz tube, placing into heating furnace, introducing CO 2 And H 2 Turning on the light source, and obtaining CO by online connected gas chromatograph 2 And concentration data of the product, thereby comparing the photo-thermal catalysis of CO by different catalysts 2 Hydrogenation activity. Wherein, 0.16% Ir-CoO/Al 2 O 3 Catalyst meterExhibits optimal CO 2 Hydrogenation activity, CH at 250 ℃ and under light conditions 4 Is produced at a rate of 128.9mmol g cat -1 h -1 . Photo-thermal catalysis of CO by different catalysts 2 The hydrogenation performance is 0.16 percent Ir-CoO/Al from high to low 2 O 3 >0.23％Ir-CoO/Al 2 O 3 >0.07％Ir-CoO/Al 2 O 3 >0.03％Ir-CoO/Al 2 O 3 >CoO/Al 2 O 3 >0.16％Ir/Al 2 O 3 。
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (16)
1. For catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 A photo-thermal catalyst, characterized in that it is used for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 The photo-thermal catalyst comprises Ir nano-particles, coO and Al 2 O 3 The carrier, ir nano particles are dispersed on the surface of CoO generated in situ, ir-CoO is inlaid in Al 2 O 3 On the nanosheets;
the catalyst is used for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 The preparation method of the photo-thermal catalyst comprises the steps of respectively synthesizing CoAl LDH and Ir nano particles by a hydrothermal method, loading the Ir nano particles on the surface of the CoAl LDH by an impregnation method, and calcining in a hydrogen atmosphere to obtain the catalyst for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 A photo-thermal catalyst;
the method for synthesizing the CoAl LDH comprises the following steps: uniformly mixing cobalt salt, aluminum salt, an organic compound and an organic solvent, and synthesizing CoAl LDH by a solvothermal method, wherein the cobalt salt is cobalt nitrate, the aluminum salt is aluminum nitrate, the organic compound is urea and ammonium fluoride, and the organic solvent is methanol;
the preparation method of the Ir nano-particles comprises the following steps: ir nano particles are synthesized by uniformly mixing iridium salt, a surfactant and an organic solvent through a solvothermal method, wherein the surfactant is polyvinylpyrrolidone PVP.
2. The method according to claim 1 for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 A photo-thermal catalyst characterized by the following composition comprising Ir-CoO/Al 2 O 3 The mass of the photo-thermal catalyst is 100%, and the Ir nano particle load is 0.03% -0.23%.
3. The method according to claim 2 for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 The photo-thermal catalyst is characterized in that the Ir nano-particle loading is 0.16%.
4. The method according to claim 1 for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 A photo-thermal catalyst characterized by comprising Al 2 O 3 The size of the nano-sheet is 2-3 mu m, the size of the Ir nano-particle is 1-2.5nm, and the size of CoO is 5-20nm.
5. Use of the catalyst according to any one of claims 1-4 for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 The preparation method of the photo-thermal catalyst is characterized in that firstly, respectively synthesizing CoAl LDH and Ir nano particles by a hydrothermal method, loading the Ir nano particles on the surface of the CoAl LDH by an impregnation method, and finally calcining in a hydrogen atmosphere to obtain the catalyst for catalyzing CO 2 Hydrogenated Ir-CoO/Al 2 O 3 Photo-thermal catalyst.
6. The method of preparing according to claim 5, wherein the method of synthesizing the CoAl LDH comprises the steps of: uniformly mixing cobalt salt, aluminum salt, an organic compound and an organic solvent, and synthesizing CoAlLDH by a solvothermal method;
the cobalt salt is cobalt nitrate, the aluminum salt is aluminum nitrate, the organic compound is urea and ammonium fluoride, and the organic solvent is methanol.
7. The process according to claim 5, wherein the amount of cobalt nitrate is 1.8 to 9mmol, the amount of aluminum nitrate is 0.9 to 4.5mmol, the amount of ammonium fluoride is 1.2 to 6mmol, the amount of urea is 5 to 25mmol, and the amount of methanol is 15 to 80mL.
8. The process of claim 5 wherein the solvothermal method is carried out at a temperature of 130-160 ℃ for a reaction time of 10-18 hours.
9. The preparation method according to claim 5, wherein the preparation method of the Ir nanoparticle comprises the steps of: uniformly mixing iridium salt, a surfactant and an organic solvent, and synthesizing Ir nano particles by a solvothermal method;
the iridium salt is one or more of iridium chloride, iridium acetate and chloroiridic acid; the surfactant is polyvinylpyrrolidone PVP; the organic solvent is ethylene glycol.
10. The method according to claim 9, wherein the iridium salt is iridium acetate; the surfactant is PVP K30.
11. The method according to claim 10, wherein iridium acetate is used in an amount of 0.01 to 0.05mmol, PVP K30 is used in an amount of 50 to 200mg and ethylene glycol is used in an amount of 10 to 40mL.
12. The preparation method according to claim 9, characterized in that the temperature of the solvothermal method for preparing the Ir nano-particles is 170-210 ℃ and the reaction time is 18-24h.
13. The preparation method according to claim 5, wherein the specific process of loading the Ir nanoparticles onto the surface of the CoAl LDH by impregnation method is as follows: dissolving the dried CoAl LDH into ethanol solution, adding Ir nanoparticle suspension, stirring at room temperature, and finally centrifugally drying to obtain the Ir/CoAl LDH.
14. The method according to claim 5, wherein the calcination temperature is 300 to 500 ℃ and the calcination time is 1 to 3 hours.
15. A process for the catalysis of CO as claimed in any of claims 1 to 4 2 Hydrogenated Ir-CoO/Al 2 O 3 Photo-thermal catalyst and/or method for catalyzing CO prepared by the method of any one of claims 5-14 2 Hydrogenated Ir-CoO/Al 2 O 3 Photo-thermal catalyst catalyzes CO under photo-thermal condition 2 Application in hydrogenation.
16. The use according to claim 15, wherein the catalytic conditions are: the light source is a xenon lamp with the wavelength of 420-780nm, the working current of 20A and the light intensity of 2W cm -2 ，CO 2 The flow rate is 4mL/min, H 2 The flow rate is 16mL/min, the reaction temperature is 100-250 ℃, and the reaction device is a gas-phase flow reactor.
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