CN114029061B - Bimetal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion - Google Patents
Bimetal efficient catalyst, preparation method and method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 64
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 229910002367 SrTiO Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- GQHZBSPNWMRGMM-UHFFFAOYSA-N [Co].[Sr] Chemical compound [Co].[Sr] GQHZBSPNWMRGMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- 238000013032 photocatalytic reaction Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052802 copper Inorganic materials 0.000 abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 150000002739 metals Chemical class 0.000 abstract description 8
- 150000001879 copper Chemical class 0.000 abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910016507 CuCo Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- -1 montmorillonite modified titanium dioxide Chemical class 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/40—
-
- 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
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
Abstract
The invention provides a bimetallic high-efficiency catalyst, a preparation method and a method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion. According to the catalyst, metals Co and Cu are loaded on the strontium titanate carrier in steps, adjacent cobalt nano particles and copper clusters are utilized, and the cooperation of Cu and carrier interface sites is utilized, so that the C-C bond cross coupling reaction is catalyzed under the photo-thermal condition, and the Co-conversion of methane and carbon dioxide into ethanol and acetaldehyde with high yield and selectivity is realized.
Description
Technical Field
The invention relates to the technical field of natural gas and carbon dioxide catalytic conversion technology and related chemistry, in particular to a bimetallic high-efficiency catalyst, a preparation method and a method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion.
Background
With the exploration of natural gas resources, unconventional natural gas reserves are found to be rich, wherein carbon-rich natural gas is an important unconventional natural gas, and CH thereof 4 :CO 2 The volume ratio of (2) is in the range of 1:0.5-1:2, the reserves are rich, but the combustion heat value is low, the exploitation place is remote, and the separation cost is high. Thus, CH 4 -CO 2 Co-transformation has received extensive attention.
CH 4 -CO 2 The cotransformation pathway can be divided into: CH (CH) 4 -CO 2 Reforming synthesis gas, CH 4 -CO 2 Co-conversion to C2 hydrocarbons and CH 4 -CO 2 Co-conversion to produce C2 oxygenate chemicals. Wherein CH is 4 -CO 2 Strong heat absorption (delta H) of reforming reaction 0 298K ＝247kJ·mol -1 ) The reaction is carried out at a higher reaction temperature (T is more than 800 ℃), the high-temperature reaction not only causes excessive rapid carbon deposition, but also causes serious deactivation of active metal components; is affected by reverse steam shift reaction to produce H of synthetic gas 2 the/CO ratio may be too low (H 2 :CO<1)；CH 4 -CO 2 Co-conversion to C2 hydrocarbons utilizing CO 2 As an oxidant for oxidative coupling of methane, needed in>The reaction is carried out at 900 ℃, the yield and the selectivity of the C2 hydrocarbon are far lower than those of the equilibrium, and the high-temperature environment of the catalytic system can aggravate the dry reforming of the side reaction methane (methane-carbon dioxide reforming) and reduce the selectivity of the C2 hydrocarbon; photo (thermal) catalysis of CH 4 -CO 2 The C2 oxygen-containing chemicals prepared by co-conversion reduces the thermodynamic barrier, avoids the deactivation of carbon deposition and sintering deactivation of the catalyst caused by high-temperature reaction, realizes the preparation of high-value chemicals by co-conversion under mild conditions, has higher atomic economy, and is a promising conversion path but is caused by CH 4 -CO 2 The restriction that the self C-H bond and the C-O bond are difficult to activate in high stability and difficult to realize in cross coupling of the C-C bond is insufficient, and the obtained results in the field of co-transformation are still insufficient, so that the value is continuously studied.
In the current research report, the photo (thermal) catalytic activation of CH 4 -CO 2 Co-conversion to produce C2 oxygenates is based on a copper-based multi-phase catalyst. For example, cu/CdS-TiO composite semiconductor is used 2 /SiO 2 Photocatalyst at 373K, space velocity 200h -1 Ultraviolet light 20.0 mW.cm -2 Under the condition of CH 4 The conversion of (2) was 1.47%, CO 2 The conversion of acetone was 0.74% and the selectivity of acetone was 92.3% (Catalysis Today,2004.98 (4): 505-509), overallThe conversion is still low. For example, under the condition of externally heating to 100 ℃, the montmorillonite modified titanium dioxide catalyst realizes CH 4 -CO 2 Co-conversion of CO, C as the product 2 H 6 、CH 3 OH and C 3 H 8 Wherein CO is 237.5mmol g of main product catal .-1 h -1 ) (Materials Research Bulletin, 2015.63:13-23), but no high values of C2 oxygenate chemicals were produced. In subsequent studies, cu modified graphitized carbonitride (g-C 3 N 4 ) Similar results were obtained for montmorillonite modified titania catalysts at 373K (Applied Surface Science, 2017.419:875-885.). For example, 0.5% Ru/Zn-g-C under conditions of 80℃with additional light 3 N 4 On-1/20 catalyst, CO, CH 3 CHO, and CH 3 CH 2 OH yields were 865.25, 330.38 and 1442.88. Mu. Mol/g (3 h) (Applied Surface Science, 2019.498:143861-143872), respectively, but overall yields and selectivities for C2 oxygenates were low, and furthermore the source mechanism for C2 oxygenates was not clear.
Patent 108822883A discloses a method for realizing photo-thermal Fischer-Tropsch synthesis by co-supporting strontium titanate with cobalt and plasma active metals, which relates to a preparation method of cobalt and plasma active metals, a dipping-sintering method or a photo-deposition-sintering method, a precursor solution containing cobalt or plasma active metals is mixed with a carrier material, and the solution is heated by an electric heating stirring table to evaporate and dry the solution in H 2 Firing reduction in an Ar mixed atmosphere, or photodecomposition of active elements on a support using concentrated simulated sunlight for light supply. However, co and Cu obtained by the preparation method are of alloy structures, and the interfacial effect of the strontium titanate carrier is not adjustable, so that the C-C coupling reaction activity is low, and the selectivity of the naturally obtained C2 oxygen-containing chemicals is low.
The source mechanism of the C2 oxygen-containing chemicals is not clearly explored, so that the high stability of the C-H bond and the C-O bond in the prior art is difficult to activate and the cross coupling of the C-C bond is difficult to realize. Therefore, aiming at the situation that the yield and selectivity of C2 oxygen-containing chemicals are low, developing a high-efficiency catalyst for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion is a problem to be solved.
Disclosure of Invention
In order to solve the problems, the invention provides a bimetallic high-efficiency catalyst for preparing carbon-rich natural gas CH 4 And CO 2 The ethanol and the acetaldehyde which are both high in yield and selectivity are jointly converted. According to the catalyst, metals Co and Cu are loaded on a carrier strontium titanate step by step, and the adjacent cobalt nano particles and copper clusters and the cooperation of Cu and carrier interface sites are utilized to efficiently catalyze the cross coupling reaction of C-C bonds under the photo-thermal condition to form target products ethanol and acetaldehyde.
The technical scheme of the invention is as follows:
the invention provides a bimetal efficient catalyst, which is characterized in that Co and active metal Cu are jointly loaded on a strontium titanate carrier, the loading amount of the Co is 1-10.0 wt% based on the mass of the strontium titanate carrier, and the loading amount of the Cu is 0.1-5.0 wt%;
the XRD pattern of the catalyst (as shown in FIG. 1 (c)) clearly observes SrTiO at diffraction angles 23+ -0.5 °, 32+ -0.5 °, 40+ -0.5 °, 46+ -0.5 °, 58+ -0.5 °, 68+ -0.5 °, 77+ -0.5 ° 3 The (100), (110), (111), (200), (211), (220) and (310) characteristic diffraction peaks of the (JCPDS 35-0734) structure;
characteristic diffraction peaks of (111), (200) and (220) of Co (JCPCDS 15-0806) were observed at diffraction angles 44+ -0.5 °, 51+ -0.5 ° and 76+ -0.5 °, indicating that Co particles were formed and crystallized well; in addition, no characteristic diffraction peak of Cu was observed, because the particle size of the formed copper clusters was too small.
Further, the strontium titanate carrier is a truncated dodecahedron with the (110) crystal face exposed.
Further, the Co is a nanoparticle, wherein the lattice spacing d=0.204 nm of Co, and the particle size is 2 to 5nm.
Further, the Cu is a copper cluster with a particle size of less than 1nm, and is uniformly dispersed around the Co nanoparticles.
Further, the active component of the catalyst consists of adjacent Co nano particles and Cu clusters, and interface sites of the Cu clusters and a strontium titanate carrier, wherein Cu of the interface sites is biased to positive valence due to the action of an oxidizing carrier.
In the catalyst disclosed by the invention, amorphous Cu clusters are uniformly dispersed around Co nano-particles, and Cu at interface sites is biased to positive valence due to strong interaction of the Cu clusters and strontium titanate. Due to the presence of part of Cu Ⅰ In the CO-conversion reaction of methane and carbon dioxide, the adsorption strength of CO after the activation of the C-O bond of the carbon dioxide is improved, and the key effect on the occurrence of further C-C coupling is played.
The invention also provides a preparation method of the catalyst, which comprises the following steps:
doping Co into strontium titanate by a hydrothermal method to form a catalyst precursor-cobalt-containing strontium titanate; then reducing cobalt in the precursor under a hydrogen atmosphere to form particles; finally, cu is reduced by deposition to form the strontium titanate loaded copper-cobalt catalyst.
Further, the method comprises the following steps:
step S1: preparation of strontium titanate SrTiCoO containing cobalt 3 ：
Preparing water and alcohols into solution, and adding C 16 H 36 O 4 Ti is added into a four-neck flask drop by drop, then alkali solution and Sr are added 2+ Solution and Co 2+ After uniformly stirring, crystallizing at 100-200 ℃, and centrifugally washing and drying after crystallization; grinding and roasting the obtained sample to obtain a catalyst precursor, namely strontium cobalt titanate SrTiCoO 3 ；
Step S2: the catalyst precursor SrTiCoO 3 Reducing for 2-4 h at 100-1000 ℃ in hydrogen atmosphere to obtain Co-SrTiO 3 I.e., co-STO;
step S3: the Co-STO liquid prepared above is transferred to a round bottom flask after being sealed, cu is added dropwise 2+ Stirring the solution continuously for 10-60 min in ice bath, centrifuging, washing, and firing the obtained precipitate in hydrogen atmosphere to obtain Cu-Co-STO.
Further, in step S1, the Sr 2+ The solution can be nitrate of SrSolution or chloride salt solution, preferably SrCl at a concentration of 0.24mol/L 2 ·6H 2 O solution.
Further, in step S1, the Co 2+ The solution may be a nitrate solution or a sulfate solution of Co, preferably Co (NO) with a concentration of 0.06mol/L 3 ) 2 ·6H 2 O solution.
Further, in step S1, the Sr 2+ 、C 16 H 36 O 4 Ti and Co 2+ The molar ratio of (2) is 4:3:1.
Further, in step S1, the SrCl 2 ·6H 2 O、C 16 H 36 O 4 Ti and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 4:3:1.
Further, in step S1, the alcohol may be ethylene glycol, ethanol, glycerol, or pentaerythritol.
Further, in the step S1, the roasting temperature of the sample is controlled to be 500-1000 ℃ and the roasting time is 2-8 h.
Further, in step S2, the catalyst precursor is placed in SrTiCoO 3 In a tube furnace, the temperature is raised from room temperature to 800 ℃ at a heating rate of 20 ℃/min, and the firing is carried out for 2 hours.
Further, in step S3, the Cu 2+ The solution may be a nitrate solution or a sulfate solution of Cu, preferably Cu (NO) at a concentration of 3.0mmol/L 3 ) 2 ·3H 2 O solution.
Further, in step S3, the Cu (NO 3 ) 2 ·3H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O was 1:20.
Further, in step S3, the temperature of firing the precipitate in a hydrogen atmosphere is 200 to 600 ℃ for 1 to 5 hours.
The biggest innovation of the catalyst preparation method of the invention is that the prior art generally refers to SrTiO which is already formed 3 Mixing carrier and metal salt solution such as nitro hydrochloric acid, chloride salt and sulfate solution of Co and Cu, dispersing uniformly, evaporating water in metal salt to dryness to obtain Co and CuSalt solution of Cu is loaded on SrTiO 3 On a carrier or Co 2+ And Cu 2+ At the same time dope SrTiO 3 In the crystal lattice of the carrier, the bimetal prepared by the two methods is of an alloy structure, and Co and Cu interface function and CuCo and SrTiO interface function 3 The interfacial effect of the carrier is not controllable, so that the catalytic activity of the carrier on the C-C coupling reaction is lower in the co-conversion reaction of methane and carbon dioxide.
In contrast, in the catalyst preparation method of the present invention, the already molded SrTiO is not directly used 3 The carrier is prepared by doping cobalt into SrTiO 3 Then reducing under hydrogen atmosphere to obtain Co-STO; and then utilizing Cu salt solution to replace metal Co through potential, and carrying out heat treatment under the hydrogen atmosphere to obtain the Cu-Co-STO. On the one hand, due to the separate doping of cobalt into SrTiO 3 In the crystal, the particle size of cobalt can be controlled, and cobalt particles with strong interaction with strontium titanate can be obtained; then selectively replacing cobalt by copper, and then secondarily reducing, wherein the interface effect of the obtained catalyst Cu and the carrier is adjustable, and the interface effect between Cu and Co is different. In the Cu-Co-STO catalyst prepared by the method, co is uniformly dispersed on a strontium titanate carrier in a nano particle mode, cu surrounds the Co nano particle in an amorphous high-dispersion cluster smaller than 1nm, two metals are respectively uniformly loaded on the strontium titanate carrier in a non-alloy structure mode, and compared with the catalyst in an alloy structure, the catalyst has higher reaction activity. On the other hand, due to the metal combination form of the non-alloy structure, part of active metal Cu is biased to positive valence at the interface site where Cu and strontium titanate carriers are contacted, and the C-C coupling reaction of the invention is promoted, thereby remarkably improving the yield and selectivity of C2 oxygen-containing chemicals.
The invention also provides a method for preparing ethanol/acetaldehyde by methane-carbon dioxide co-conversion, which comprises the following steps:
adding the catalyst and deoxidized deionized water into a photocatalysis reaction kettle by adopting a photocatalysis method, firstly filling nitrogen to replace air in the reaction kettle, and filling reaction gas CH 4 And CO 2 The gas pressure is kept at 0.1-1 Mpa, and the temperature is kept at room temperatureAnd (3) heating to the reaction temperature of 80-200 ℃, then starting a light source, controlling the reaction time to be 0.5-12 h, and cooling to room temperature after the reaction is finished to obtain the ethanol and the acetaldehyde.
Further, the catalyst is added in an amount of 0.1 to 10mg/mL based on the volume of deionized water in the reaction system.
Further, the dosage of the deoxidized deionized water is 5-100 mL.
Further, the light source is a 300W full-wave-band xenon lamp light source.
Further, using gas chromatography, C 2 H 5 The yield of OH is 200-800 mu mol g -1 ·h -1 ，CH 3 The yield of CHO is 50-500 mu mol g -1 ·h -1 The total selectivity of C2 oxygen-containing chemicals is up to more than 80%.
The technical scheme of the invention has the following beneficial effects:
1. the catalyst of the invention has different structure from the common alloy in the prior art, the carrier strontium titanate is a truncated dodecahedron with exposed (110) crystal face, and the active component consists of adjacent Co nano particles and copper clusters, and interface sites of the copper clusters and strontium titanate carrier. Due to the synergistic effect of adjacent cobalt nano particles and copper clusters and Cu and carrier interface sites, the catalytic activity of the C-C coupling reaction is improved.
2. The preparation method has the advantages of simple and controllable process conditions and low energy consumption. The Co and Cu are doped into the lattice structure of the carrier in sequence by adjusting the composition of raw materials, the addition sequence and the reaction condition, and are not simultaneously loaded on the interface of the carrier, so that the interaction between the active metals and the interface action between the active metals and the carrier are regulated. In addition, at the interface site between Cu and carrier, positive valence Cu plays a critical role in C-C coupling, and improves the yield and selectivity of C2 oxygen-containing chemicals. Compared with the preparation method in the prior art, the preparation method has obvious progress in two aspects of energy consumption and yield, reduces the production cost, and increases the yield and selectivity of high-added-value products. Therefore, the preparation method has a certain commercialized prospect.
3. Methane-dioxide according to the inventionThe method for preparing ethanol/acetaldehyde by carbon CO-conversion is to perform gas-solid-liquid three-phase reaction, add deoxidized deionized water, and utilize the deoxidized deionized water to generate activity H and activity OH by photolysis under the condition of illumination and external heat source, wherein the activity H is opposite to CO 2 Reduction of OH to CH 4 Oxidation is carried out and then activated CO 2 And CH (CH) 4 Coupling reaction occurs to produce ethanol and acetaldehyde. The prior art is generally a gas-solid reaction in which the hydrogen source content is far from sufficient, reducing the possibility of coupling to form C2 oxygenates.
Drawings
FIG. 1 (a) hydrothermal SrTiCoO synthesis method synthesized in example 1 of the present invention 3 The method comprises the steps of carrying out a first treatment on the surface of the XRD patterns of (b) Co-STO and (c) Cu-Co-STO. Wherein the abscissa is 2θ, units: a degree; the ordinate is intensity.
FIG. 2 (a) shows a Cu-Co-STO in example 1 of the present invention; and (b) is a transmission electron micrograph of CuCo-STO in comparative example 1.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A bimetallic high-efficiency catalyst is characterized in that Co and active metal Cu are jointly loaded on a strontium titanate carrier, the loading of Co is 9.5wt% and the loading of Cu is 0.5wt% based on the mass of the strontium titanate carrier.
The preparation method comprises the following steps:
step S1: adding water and glycol into a four-neck flask to prepare a uniform solution, and adding C 16 H 36 O 4 Ti (0.18 mmol) was added dropwise to the flask; subsequently 30mL of LiOH H was added 2 O (3.0 mol/L) solution and 10mL Sr 2+ -Co 2+ Solution (0.24 mol/L SrCl) 2 ·6H 2 O and 0.06mol/L Co (NO) 3 ) 2 ·6H 2 O); stirring for 30 minutes, transferring to a hydrothermal kettle, and crystallizing in a blowing drying oven at 180 ℃ for 48 hours; centrifugal washing after crystallization, and drying overnight; grinding the obtained sample, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst precursor, namely strontium cobalt titanate SrTiCoO 3 ；
Step S2: srTiCoO 3 Firing 2h at a rate of 20 ℃/min from room temperature to 800 ℃ under a hydrogen atmosphere to obtain Co-STO.
Step S3: the Co-STO liquid prepared above was sealed and transferred to a round-bottomed flask, and Cu (NO 3 ) 2 ·3H 2 O,10mL of deionized water is dissolved and dispersed in an ultrasonic manner to prepare a copper nitrate solution with the concentration of 3.0mmol/L, the copper nitrate solution is dripped into a flask, stirring is continued for 30min under ice bath, and then the obtained precipitate is subjected to centrifugation, washing with deionized water and drying, and is fired for 1h at 400 ℃ in a hydrogen atmosphere, so that the catalyst Cu-Co-STO is prepared.
As can be seen from the XRD spectra of FIG. 1, in FIG. 1 (a), srTiO can be clearly observed at 22.78 °, 32.42 °, 39.98 °, 46.48 °, 57.79 °, 67.80 ° and 77.18 ° 3 The diffraction peaks characteristic of the (100), (110), (111), (200), (211), (220) and (310) structures of (JCPDS 35-0734) and no SrTiO removal was observed in the XRD pattern 3 Other hetero-phases are due to the TiO of Co substituting part of Ti and entering strontium titanate 6 In the lattice of octahedra.
After being subjected to hydrogen heat treatment at 800 ℃, the sample crystal phase structure is as shown in FIG. 1 (b) and FIG. 1 (c), except for SrTiCoO 3 Characteristic peaks of (111), (200) and (220) of Co (JCPDS 15-0806) were observed at 44.22 DEG, 51.52 DEG and 75.85 DEG, indicating SrTiCoO 3 The cobalt in (c) was reduced, and it was estimated that Co particles were formed and crystallized well. In addition, no characteristic diffraction peak of Cu was observed, because the particle size of the formed copper clusters was too small.
What needs to be explained here is: a specific crystalline phase structure will exhibit a corresponding diffraction peak, for example, the diffraction peak of strontium titanate corresponds to the mark position of fig. 1; when the metal is loaded, XRD can simultaneously generate diffraction peaks of the metal and strontium titanate, such as diffraction peak positions of marked cobalt, but copper is not observed because the particle size of the copper is too small and is lower than the detection limit of an instrument, so that the copper is just the cluster structure.
Thus, the catalyst support structure is essentially unchanged, while Co forms uniform nanoparticles, cu clusters are highly dispersed.
Comparative example 1
The CuCo-STO of comparative example 1 was Co and active metal Cu were jointly supported on a strontium titanate support, the Co loading was 7.5wt% and the Cu loading was 2.5wt% based on the mass of the strontium titanate support.
The preparation method comprises the following steps:
step A: adding water and glycol into a four-neck flask to prepare uniform solution A, adding C 16 H 36 O 4 Ti (0.18 mmol) was added dropwise to the flask; subsequently 30mL of LiOH H was added 2 O (3.0 mol/L) solution and 10mL Sr 2+ -Co 2+ -Cu 2+ Solution (0.24 mol/L SrCl) 2 ·6H 2 O、0.48mol/L Co(NO 3 ) 2 ·6H 2 O and 0.12mol/L Cu (NO) 3 ) 2 ·6H 2 O); stirring for 30min, transferring to a hydrothermal kettle, crystallizing in a blowing drying oven at 180 ℃ for 48h, centrifuging and washing after crystallization, and drying overnight; grinding the obtained sample, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst precursor SrTiCuCoO 3 ；
And (B) step (B): the precursor SrTiCuCoO 3 And (3) firing for 2 hours from room temperature to 800 ℃ at a heating rate of 20 ℃/min in a hydrogen atmosphere to obtain the CuCo-STO, wherein Cu and CO are in an alloy structure.
As shown in FIG. 2, (a) is a transmission electron microscope image of Cu-Co-STO in example 1, and (b) is a transmission electron microscope image of CuCo-STO in comparative example 1, the morphology and statistical particle size distribution of the samples were determined by TEM and HRTEM, and the metal particles of Cu-Co-STO and CuCo-STO after hydrogen reduction were uniformly distributed and have similar particle sizes.
For Cu-Co-STO, by measuring the lattice fringes of the metal particles anchored on the strontium titanate surface in the HRTEM image, the measured lattice spacing d=0.204 nm, which is determined as Co (111), an amorphous structure was found in the vicinity of the Co particles, and it was inferred that Cu formed amorphous highly dispersed small clusters after substitution reduction, which was shown as Cu clusters appearing around the Co particles with high dispersion.
For CuCo-STO x CuCo-STO was measured by measuring lattice fringes of metal particles anchored on the strontium titanate surface in the HRTEM image x Is 0.209nm, it is inferred that CuCo alloy nanoparticles were formed.
Comparative example 2
Co-STO of comparative example 2, co was supported on a strontium titanate support at a Co loading of 10.0wt% based on the mass of the strontium titanate support.
The preparation method comprises the following steps:
step S1: adding water and glycol into a four-neck flask to prepare a uniform solution, and adding C 16 H 36 O 4 Ti (0.18 mmol) was added dropwise to the flask; subsequently 30mL of LiOH H was added 2 O (3.0 mol/L) solution and 10mL Sr 2+ -Co 2+ Solution (0.24 mol/L SrCl) 2 ·6H 2 O and 0.60mol/L Co (NO) 3 ) 2 ·6H 2 O); stirring for 30 minutes, transferring to a hydrothermal kettle, and crystallizing in a blowing drying oven at 180 ℃ for 48 hours; centrifugal washing after crystallization, and drying overnight; grinding the obtained sample, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst precursor, namely strontium cobalt titanate SrTiCoO 3 ；
Step S2: srTiCoO 3 Firing 2h at a rate of 20 ℃/min from room temperature to 800 ℃ under a hydrogen atmosphere to obtain Co-STO.
Comparative example 3
The catalyst of comparative example 3 was a strontium titanate STO support.
Step A: adding water and glycol into a four-neck flask to prepare uniform solution A, adding C 16 H 36 O 4 Ti (0.18 mmol) was added dropwise to the flask; subsequently, 30mL of LiOH (3 mol/L) and 10mL of SrCl were added 2 ·6H 2 O (0.24 mol/L) solution; stirring for 30min, transferring to a hydrothermal kettle, crystallizing in a blowing drying oven at 180 ℃ for 48h, centrifuging and washing after crystallization, and drying overnight; grinding the obtained sample, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst precursor, namely SrTiO 3 。
And (B) step (B): srTiO 3 Firing for 2h from room temperature to 800 ℃ at a heating rate of 20 ℃/min under a hydrogen atmosphere to obtain STO.
Comparative example 4
Step A: adding water and glycol into a four-necked flaskConfigured as a homogeneous solution A, C 16 H 36 O 4 Ti (0.18 mmol) was added dropwise to the flask; subsequently, 30mL of LiOH (3 mol/L) and 10mL of SrCl were added 2 ·6H 2 O (0.24 mol/L) solution; stirring for 30min, transferring to a hydrothermal kettle, crystallizing in a blowing drying oven at 180 ℃ for 48h, centrifuging and washing after crystallization, and drying overnight; grinding the obtained sample, roasting in a muffle furnace at 550 ℃ for 4 hours to obtain a catalyst precursor, namely SrTiO 3 。
And (B) step (B): srTiO prepared by the method 3 Uniformly dispersed in a round-bottomed flask, 10mL of Co was prepared 2+ -Cu 2+ Solution (0.48 mol/L Co (NO) 3 ) 2 ·6H 2 O and 0.12mol/L Cu (NO) 3 ) 2 ·6H 2 O) a solution; under alkaline conditions (ph=9.0), the mixture was added dropwise to a flask, and the resulting precipitate was then centrifuged, washed with deionized water, and dried, and fired at 800 ℃ for 2 hours in a hydrogen atmosphere to prepare a catalyst CuCo/STO.
Test case
The catalysts prepared in example 1 and comparative examples 1 to 4 of the present invention were respectively subjected to the following photo-thermal catalytic method, the final yields of the products were analyzed by gas chromatography, and the selectivities were calculated, and the experimental results are summarized in table 1:
adding 50mg of catalyst and 50mL of deoxidized deionized water into a photocatalysis reaction kettle by adopting a photocatalysis method, firstly filling nitrogen to replace air in the reaction kettle, and introducing reaction gas CH 4 And CO 2 The gas pressure is kept at 1MPa, the light source is started after the temperature is raised to 80 ℃ from the room temperature, the reaction time is controlled to be 4 hours, and the reaction is cooled to the room temperature after the reaction is finished.
TABLE 1 results of catalytic Activity experiments for the catalysts of example 1 and comparative examples 1-4
| C 2 H 5 OH yield (g) -1 ·h -1 ) | CH 3 CHO yield (g) -1 ·h -1 ) | C2 oxygen-containing chemical Total Selectivity (%) | |
| Example 1 | 649.8 | 180.9 | 86.2 |
| Comparative example 1 | 207.1 | 70.3 | 59.1 |
| Comparative example 2 | 40.3 | 30.2 | 28.2 |
| Comparative example 3 | 0 | 0 | 0 |
| Comparative example 4 | 10.1 | 15.9 | 12.4 |
The invention provides a Cu-Co-STO with adjacent Co particles and Cu clusters x Catalyst and produced by photolysis of waterScheme of active oxygen/hydrogen activation methane/carbon dioxide. Modulation of Cu and Co geometric structures and regulation of Cu surface electronic structures realize CH 4 -CO 2 Wherein the yield of C2 oxygenate is up to 830.7. Mu. Mol h -1 g -1 Selectivity was 81.6%; by characterization and analysis of structure-activity relationship, co particles are proved to promote CH 4 Activation to form-CH 3 ，Cu 0 And Cu 1 Is synergistic in promoting CO 2 Generation of-CHO/-CH 2 OH, adjacent Co particles and Cu clusters promote-CH 3 and-CHO/-CH 2 C-C coupling of OH yields C2 oxygenate chemicals.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (8)
1. The bimetallic high-efficiency photo-thermal catalyst for preparing ethanol/acetaldehyde by methane-carbon dioxide Co-conversion is characterized in that Co and active metal Cu are jointly loaded on a strontium titanate carrier, the loading amount of Co is 1-10.0wt% based on the mass of the strontium titanate carrier, and the loading amount of Cu is 0.1-5.0wt%;
in XRD pattern of the catalyst, srTiO is arranged at diffraction angles of 23+/-0.5 degrees, 32+/-0.5 degrees, 40+/-0.5 degrees, 46+/-0.5 degrees, 58+/-0.5 degrees, 68+/-0.5 degrees and 77+/-0.5 degrees 3 The (100), (110), (111), (200), (211), (220) and (310) characteristic diffraction peaks of JCPDS 35-0734;
characteristic diffraction peaks of (111), (200) and (220) of Co JCPDS15-0806 at diffraction angles of 44+ -0.5 DEG, 51+ -0.5 DEG and 76+ -0.5 DEG;
the strontium titanate carrier is a truncated dodecahedron with a (110) crystal face exposed;
the preparation method of the catalyst adopts a hydrothermal method, and Co is doped into strontium titanate to form a catalyst precursor-strontium titanate containing cobalt; then reducing cobalt in the precursor under a hydrogen atmosphere to form particles; finally, reducing Cu by deposition to form the bimetallic high-efficiency catalyst;
the preparation method of the catalyst comprises the following steps:
step S1: preparation of strontium titanate SrTiCoO containing cobalt 3 ：
Preparing water and alcohols into solution, and adding C 16 H 36 O 4 Ti is added into a four-neck flask drop by drop, then alkali solution and Sr are added 2+ Solution and Co 2+ After uniformly stirring, crystallizing at 100-200 ℃, and centrifugally washing and drying after crystallization; grinding and roasting the obtained sample to obtain a catalyst precursor, namely strontium cobalt titanate SrTiCoO 3 ；
Step S2: the catalyst precursor SrTiCoO 3 Reducing for 2-4 h at 100-1000 ℃ in hydrogen atmosphere to obtain Co-SrTiO 3 I.e., co-STO;
step S3: the Co-STO liquid prepared above is transferred to a round bottom flask after being sealed, cu is added dropwise 2+ Stirring the solution continuously for 10-60 min in ice bath, centrifuging, washing, and firing the obtained precipitate in hydrogen atmosphere to obtain Cu-Co-STO.
2. The catalyst of claim 1, wherein the Co is a nanoparticle, wherein the Co has a lattice spacing d = 0.204nm and a particle size of 2 to 5nm.
3. The catalyst of claim 1 or 2, wherein the Cu is copper clusters having a particle size of less than 1nm, uniformly dispersed around the Co nanoparticles.
4. The catalyst of claim 1 or 2, wherein the active component of the catalyst consists of adjacent Co nanoparticles and Cu clusters, and Cu clusters and strontium titanate support interface sites, wherein the Cu of the interface sites is biased towards a positive valence due to the action of the oxidizing support.
5. A process for the preparation of a catalyst as claimed in any one of claims 1 to 4, comprising the steps of:
step S1: preparation of strontium titanate SrTiCoO containing cobalt 3 ：
Preparing water and alcohols into solution, and adding C 16 H 36 O 4 Ti is added into a four-neck flask drop by drop, then alkali solution and Sr are added 2+ Solution and Co 2+ After uniformly stirring, crystallizing at 100-200 ℃, and centrifugally washing and drying after crystallization; grinding and roasting the obtained sample to obtain a catalyst precursor, namely strontium cobalt titanate SrTiCoO 3 ；
Step S2: the catalyst precursor SrTiCoO 3 Reducing for 2-4 h at 100-1000 ℃ in hydrogen atmosphere to obtain Co-SrTiO 3 I.e., co-STO;
step S3: the Co-STO liquid prepared above is transferred to a round bottom flask after being sealed, cu is added dropwise 2+ Stirring the solution continuously for 10-60 min in ice bath, centrifuging, washing, and firing the obtained precipitate in hydrogen atmosphere to obtain Cu-Co-STO.
6. The method according to claim 5, wherein in step S1, the Sr 2+ 、C 16 H 36 O 4 Ti and Co 2+ The molar ratio of (2) is 4:3:1.
7. The method according to claim 6, wherein in step S1, the temperature of the sample calcination is controlled to be 500-1000, and the time of the calcination is controlled to be 2-8 hours.
8. A process for the co-conversion of methane-carbon dioxide to ethanol/acetaldehyde, comprising the steps of:
adding the catalyst of any one of claims 1-4 and deoxidized deionized water into a photocatalytic reaction kettle by adopting a photocatalytic method, firstly filling nitrogen to replace air in the reaction kettle, and filling a reaction gas CH 4 And CO 2 The gas pressure is kept at 0.1-1 Mpa, the temperature is raised to 80-200 ℃ from room temperature, then the light source is started, the reaction time is controlled to be 0.5-12 h, and the reaction is reversedAfter the end, cooling to room temperature to obtain ethanol and acetaldehyde.
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