CN113368852B - Preparation method and application of carbon-supported Ir-based alloy catalyst with high hydrogenation selectivity - Google Patents
Preparation method and application of carbon-supported Ir-based alloy catalyst with high hydrogenation selectivity Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 47
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000006229 carbon black Substances 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 22
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 229910009112 xH2O Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
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- 239000002245 particle Substances 0.000 abstract description 40
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000002923 metal particle Substances 0.000 abstract description 9
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 22
- 229910000510 noble metal Inorganic materials 0.000 description 13
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 11
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- 238000003917 TEM image Methods 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 8
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- 238000005054 agglomeration Methods 0.000 description 6
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
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- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015711 MoOx Inorganic materials 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
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- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention belongs to the technical field of selective hydrogenation, and particularly relates to a preparation method and application of a carbon-supported Ir-based alloy catalyst with high hydrogenation selectivity, wherein the carbon-supported Ir-based alloy catalyst with Ir-M alloy particles uniformly supported on the surface of carbon black is synthesized by a one-step solvothermal method, so that the method is simple, the reaction condition is relatively mild, the reaction environment is not harsh, and no special atmosphere is needed; the used carrier carbon black is provided with more oxygen-containing groups, so that metal salt can be fixed, the reduction of the metal salt is promoted to obtain smaller particles, the diameter of the obtained catalyst product particles is small, the effective catalytic area is larger, the metal particles are not easy to run off, and the catalytic activity of metal is better and more stable. In the aspect of catalytic performance, the catalyst prepared by the invention can be used for catalyzing and hydrogenating the cinnamyl aldehyde at normal temperature, has excellent performance, excellent catalytic activity and unsaturated alcohol selectivity, good cycle performance and good application prospect in hydrogen storage and hydrogenation dehydrogenation.
Description
Technical Field
The invention belongs to the technical field of selective hydrogenation, and particularly relates to a preparation method and application of a carbon-supported Ir-based alloy catalyst with high hydrogenation selectivity.
Background
In recent years, selective hydrogenation of α, β -unsaturated aldehydes to obtain relatively single products has been a focus of research, because both C ═ C double bond hydrogenation products and C ═ O double bond hydrogenation products can be used in the fields of reaction intermediates, perfumes, food processing, and the like. Since thermodynamically C ═ O double bonds are more stable than C ═ C double bonds, hydrogenation of C ═ O bonds with high selectivity to give unsaturated alcohols remains a problem. For example, the selective formation of 3-aminostyrene from 3-nitrostyrene is very important but it is difficult to achieve a highly selective reaction.
Ir-based noble metals and their alloys are commonly used for selective catalytic hydrogenation. However, pure Ir particles catalyze the hydrogenation of alpha, beta-unsaturated aldehyde, so that a single product is difficult to obtain. When added to a suitable support, supported Ir particles can exhibit higher C ═ O double bond hydrogenation selectivity, but still cannot meet practical requirements. While doping non-noble metals to form novel alloys is a common means for improving hydrogenation selectivity, but iridium metal salts are difficult to reduce, so that ultra-small Ir-M (M is a non-noble metal element) nanoparticles are rarely reported. It is therefore necessary to find a suitable method for synthesizing ultra-small Ir-based nanoparticles for selective hydrogenation of α, β -unsaturated aldehydes.
Carbon Black (CB) is widely used in heterogeneous catalysis due to its advantages of low price, large specific surface area, high porosity, high stability, etc., and when noble metal is compounded with carbon black, since carbon black contains many oxygen-containing groups, metal reduction can be promoted to form smaller nanoparticles.
At present, some reports exist on the research of applying the supported Ir nanoparticles to selective hydrogenation. For example, if Ir particles are supported on different oxide supports to catalyze the selective hydrogenation of crotonaldehyde, suitable oxide supports such as ReOx and MoOx have been found to increase the hydrogenation rate and yield of unsaturated alcohol, and through subsequent infrared characterization and control experiments, ReOx has been found to activate C ═ O and reduce the possibility of C ═ C double bond hydrogenation, however, the supported Ir nanoparticles have not been much improved in catalytic performance and cannot achieve both high substrate conversion and high product selectivity. In addition, research and synthesis of Ir/MgO catalyst and addition of Fe salt to improve selectivity of unsaturated alcohol have also been carried out, and subsequent research finds that after the Fe salt is added, high-valence Fe ions can promote hydrogen heterolysis to generate H+And H-The negatively charged O and the positively charged C atoms in the aldehyde groups are preferentially hydrogenated, thereby increasing the yield of the unsaturated alcohol.
Although some supported Ir nanoparticle catalysts for selective hydrogenation are synthesized at present, the synthesis conditions of the catalysts are harsh, most of the catalysts are prepared by utilizing monometallic Ir nanoparticles to support particles on a carrier in a mechanical stirring mode, the catalysts can improve the hydrogenation selectivity of alpha, beta-unsaturated aldehyde, but still hardly meet the requirements of high substrate conversion rate and unsaturated alcohol selectivity, and the metal and the carrier are only physically adsorbed and do not interact with each other, so the catalyst is easy to drop, agglomerate or deform in the catalytic process, and the self-circulation is difficult to guarantee. Meanwhile, the finally obtained catalyst particles are still not small enough, and catalytic hydrogenation can be carried out under severe reaction conditions. In addition, the direction in which the monometallic Ir catalyst can be expanded and improved is limited, and it is difficult to develop a more excellent catalyst. Therefore, it is necessary to develop a simple and efficient method for reducing an Ir salt and alloying it with other non-noble metal salts, and uniformly distributing it on a carrier, so that the obtained catalyst can be selectively hydrogenated with high efficiency, and has good catalytic activity and hydrogenation selectivity, and recyclability.
Disclosure of Invention
In order to overcome the defects of the prior art, the carbon-supported Ir-based alloy catalyst (IrM/CB) is prepared by uniformly dispersing Ir-M alloy on the surface of carbon black through a one-step method, the catalyst is applied to selective hydrogenation, alpha, beta-unsaturated aldehyde can be catalytically hydrogenated at normal temperature to obtain an unsaturated alcohol product with high yield, the catalyst has ideal circulation capacity, the catalytic activity and the selectivity are far superior to those of carbon-supported pure Ir nanoparticles, and the catalyst has good application prospects in hydrogen storage and hydrogenation dehydrogenation.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a carbon-supported Ir-based alloy catalyst comprises the following steps: IrCl is added to ethylene glycol3·xH2Stirring O, metal precursor salt, Citric Acid (CA) and carbon black at room temperature, and performing ultrasonic treatment to obtain a clear brown yellow solution; and then placing the brown yellow solution at 160-180 ℃ in a sealed state for heating reaction for 5-6 h, naturally cooling, washing and centrifugally collecting to obtain the brown yellow solution.
Preferably, IrCl3·xH2The dosage ratio of O, metal precursor salt, citric acid, carbon black and glycol is as follows:
IrCl3·xH20.05 to 0.1mmol of O, 0.025 to 1mmol of metal precursor salt, 96 to 192mg of citric acid, 50 to 100mg of carbon black, and 12 to 18mL of ethylene glycol.
The synthesis method is suitable for various non-noble metal salts, and the hydrogenation performance of the cinnamaldehyde catalyzed by most bimetallic alloy catalysts is better than that of single metal Ir/CB. Preferably, the metal precursor salt includes, but is not limited to, CdCl2、Ga(acac)2、InCl3、ZnCl2、SnCl4·5H2O。
Further, the metal precursor salt is CdCl2、Ga(acac)2。
Specifically, the metal precursor salt is CdCl2. The invention obtains the IrCd/CB with the most preferable selective hydrogenation performance by regulating and controlling proper non-noble metal species.
The invention skillfully utilizes the characteristic that glycol can be used as a solvent and a reducing agent, and adopts a one-step solvothermal method to reduce Ir-M (including Cd, Ga, In, Zn, Sn and the like) double metal salt into Ir-M alloy which is uniformly dispersed on the surface of carrier carbon black, and because oxygen-containing groups on the carbon black can adsorb and stabilize the metal salt, the formation of small particles is promoted, and the interaction between metal particles and the carrier can be enhanced, the prepared carbon-loaded Ir-based alloy catalyst (IrM/CB) structure can enlarge the contact area of active catalytic sites, improve the stability of the catalyst and improve the hydrogenation selectivity of the Ir-M alloy to unsaturated aldehyde.
The invention synthesizes an IrM/CB structure with Ir-M nano particles evenly distributed on carbon black in one step by a simple solvothermal method, the nano particles have small size, the synthesis is simple, the reaction conditions are not harsh, and a large amount of catalysts can be synthesized at one time; it can be found through various characterizations that the non-noble metal element M is capable of reducing and alloying with Ir; the obtained IrM/CB is used for catalytic hydrogenation of cinnamaldehyde, the reaction can be carried out at normal temperature, the reaction condition is mild, and the catalytic activity and the cinnamyl alcohol selectivity are better than those of pure Ir/CB; the IrCd/CB catalyst can catalyze and hydrogenate cinnamyl aldehyde at normal temperature, has 99.8 percent of conversion rate and 94.1 percent of cinnamyl alcohol selectivity after 11 hours, and has performance far superior to that of single metal Ir/CB; the catalyst synthesized by the method is proved to have excellent performance for selective hydrogenation of alpha, beta-unsaturated aldehyde, and is expected to have good application prospect in hydrogen storage and hydrogenation dehydrogenation.
In addition, it is presumed that other bimetallic iridium-based nanomaterials have the same catalytic activity, that is, other bimetallic iridium-based alloy catalysts have the same good catalytic hydrogenation or hydrogen storage activity.
Preferably, the reaction temperature is 160 ℃ and the reaction time is 5 h.
Preferably, the room temperature is 20-30 ℃, the stirring speed is 400-600rpm, and the stirring and ultrasonic time is 0.5-1 h.
Further, the room temperature was 25 ℃, the stirring speed was 500rpm, and the stirring and sonication time was 0.5 h.
The invention also provides the carbon-supported Ir-based alloy catalyst prepared by the method.
The invention also provides application of the carbon-supported Ir-based alloy catalyst in selective hydrogenation reaction of alpha, beta-unsaturated aldehyde.
Preferably, the α, β -unsaturated aldehyde includes, but is not limited to, cinnamaldehyde.
Preferably, the carbon-supported Ir-based alloy catalyst of the present invention can also be applied in the field of hydrogen storage and dehydrogenation (i.e., having hydrogen storage and dehydrogenation functions).
Compared with the prior art, the invention has the beneficial effects that:
the iridium-based bimetallic alloy synthesized by the existing method needs relatively violent synthesis conditions, generally needs to be heated to more than 200 ℃ or uses a strong reducing agent, has certain danger, and is not energy-saving and environment-friendly. Meanwhile, the Ir particles synthesized by the existing method have no good anchoring sites, so that the obtained particles are large, the catalytic activity is weak, and the Ir particles are easy to fall off or deform in the catalytic process. The preparation method of the carbon-supported Ir-based alloy catalyst provided by the invention is simple, the carbon-supported Ir-based alloy catalyst with Ir-M alloy particles uniformly supported on the surface of carbon black can be synthesized by only one-step solvothermal method, the used glycol is a solvent and a reducing agent, citric acid is used as a stabilizing agent, the reaction conditions are relatively mild, and the reaction environment is not harsh and does not need special atmosphere; the used carrier carbon black is provided with more oxygen-containing groups, so that metal salt can be fixed, the reduction of the metal salt is promoted to obtain smaller particles, the diameter of the obtained catalyst product particles is small, the effective catalytic area is larger, the metal particles are not easy to run off, and the catalytic activity of metal is better and more stable. In the aspect of catalytic performance, the catalyst prepared by the invention can be used for catalyzing and hydrogenating the cinnamyl aldehyde at normal temperature, has excellent performance, excellent catalytic activity and unsaturated alcohol selectivity, good cycle performance and good application prospect in hydrogen storage and hydrogenation dehydrogenation.
Drawings
FIG. 1 is a TEM image of IrCd/CB;
FIG. 2 is a particle size diagram of IrCd/CB;
FIG. 3 is a high angle annular dark field scanning TEM image and element mapping image of IrCd/CB;
FIG. 4 is a TEM image of IrGa/CB;
FIG. 5 is a graph showing the particle size of IrGa/CB;
FIG. 6 is a TEM image and element mapping image of high angle annular dark field scanning of IrGa/CB;
FIG. 7 is a TEM image of IrSn/CB;
FIG. 8 is a particle size diagram of IrSn/CB;
FIG. 9 is a TEM image of IrZn/CB;
FIG. 10 is a graph of IrZn/CB particle size;
FIG. 11 is a TEM image of IrIn/CB;
FIG. 12 is a particle size diagram of IrIn/CB;
FIG. 13 is a TEM image of Ir/CB;
FIG. 14 is a particle size plot of Ir/CB;
FIG. 15 is an XRD pattern of Ir/CB, IrCd/CB, IrGa/CB, IrSn/CB, IrZn/CB, Irin/CB;
FIG. 16 is a schematic of the hydrogenation of cinnamaldehyde;
FIG. 17 is a comparison of results for various Ir-based catalysts for the hydrogenation of cinnamaldehyde;
FIG. 18 shows the conversion and selectivity of IrCd/CB catalyst for cinnamaldehyde hydrogenation;
FIG. 19 shows the conversion and selectivity of IrGa/CB catalyst for the hydrogenation of cinnamaldehyde;
FIG. 20 shows the results of multiple catalytic hydrogenations of cinnamaldehyde with IrCd/CB catalyst;
FIG. 21 is an XPS spectrum of Ir in Ir/CB and IrCd/CB catalysts;
FIG. 22 is an XPS spectrum of Cd in IrCd/CB catalyst.
Detailed Description
The following further describes embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Interpretation of terms:
the Ir-based alloy is formed by fixing metal iridium and adding other non-noble metals into the fixed iridium to form IrCd, IrGa, IrSn and other alloys.
α, β -unsaturated aldehyde: aldehydes having unsaturated bonds in the alpha, beta positions attached to the aromatic ring, the catalytic substrate primarily used in the present invention is cinnamaldehyde.
Selective hydrogenation: the organic substrate is subjected to catalytic hydrogenation at a certain temperature and under hydrogen pressure to selectively break C ═ O double bonds or other unsaturated bonds.
XRD: x-ray powder diffraction.
TEM: transmission electron microscopy.
SEM: and (3) carrying out a field emission scanning electron microscope.
XPS: x-ray electron energy spectrum.
EXAMPLE 1 preparation of IrCd/CB heterogeneous catalyst
15mg of IrCl3·xH2O(0.05mmol)、184mg CdCl2(1mmol), 96mg CA, 50mg carbon black and 12mL ethylene glycol were added to a 20mL glass vial, stirred vigorously (500 rpm speed) at 25 ℃ for 0.5 hour at room temperature and sonicated for 0.5 hour (360W) to give a clear tan solution. And then sealing the glass bottle, heating the glass bottle in an oil bath kettle at 160 ℃ for reaction for 5 hours, naturally cooling the glass bottle to room temperature, washing the product once by using water and absolute ethyl alcohol in sequence, centrifuging the product (the rotating speed is 8000r/min), collecting the product, and drying the product in an oven at 60 ℃ for 12 hours to obtain IrCd/CB.
TEM test and particle size measurement of IrCd/CB were carried out, and as shown in FIG. 1, it was found that the metal particles were uniformly distributed on the carbon black, and no agglomeration was found. As shown in FIG. 2, the average particle size of the IrCd/CB alloy particles was 1.6 nm.
TEM test and element distribution analysis of high-angle annular dark-field scanning (high-angle annular dark-field scanning) are performed on IrCd/CB, as shown in a TEM image and an element mapping image of FIG. 3, and the distribution positions of Ir and Cd are basically the same, so that the formation of IrCd alloy is proved.
Example 2 preparation of IrGa/CB
The preparation method is the same as IrCd/CB except that 184mg CdCl is added2(1mmol) was replaced by 18.5mg Ga (acac)2(0.05mmol) to prepare IrGa/CB.
TEM test and particle size measurement were performed on IrGa/CB, and as shown in FIG. 4, the metal particles were found to be uniformly distributed on the carbon black, and no agglomeration was found. As shown in FIG. 5, the average particle diameter of the IrGa/CB alloy particles is 1.6 nm.
A TEM test and an element distribution analysis of high-angle annular dark-field scanning (high-angle annular dark-field scanning) were performed on IrGa/CB, as shown in the TEM image and the element mapping image of fig. 6, and it can be seen that Ir and Ga element distribution positions are substantially the same, confirming that the IrGa alloy was formed.
Example 3 preparation of IrSn/CB
The preparation method is the same as IrCd/CB except that 184 is addedmg CdCl2(1mmol) was replaced by 8.8mg SnCl4·5H2O (0.05mmol), IrSn/CB was prepared.
TEM test and particle size measurement were performed on IrSn/CB, and as shown in FIG. 7, the metal particles were found to be uniformly distributed on the carbon black, and no agglomeration was found. As shown in FIG. 8, the average particle diameter of the IrSn/CB alloy particles is 1.3 nm.
Example 4 preparation of IrZn/CB
The preparation method is the same as IrCd/CB except that 184mg CdCl is added2(1mmol) was replaced by 3.4mg ZnCl2(0.025mmol) to obtain IrZn/CB.
TEM test and particle size measurement were performed on IrZn/CB, as shown in FIG. 9, and it was found that the metal particles were uniformly distributed on the carbon black, and no agglomeration was found. As shown in FIG. 10, the average particle diameter of the IrZn/CB alloy particles was 1.8 nm.
Example 5 preparation of IrIn/CB
The preparation method is the same as IrCd/CB except that 184mg CdCl is added2(1mmol) was replaced by 11.1mg InCl3(0.05mmol) to prepare IrIn/CB.
TEM test and particle size measurement were performed on IrIn/CB, as shown in FIG. 11, and it was found that the metal particles were uniformly distributed on the carbon black, and no agglomeration was found. As shown in FIG. 12, the average particle diameter of the IrIn/CB alloy particles was 1.5 nm.
Comparative example 1 Ir/CB preparation
15mg of IrCl3·xH2O (0.05mmol), 96mg CA, 50mg carbon black and 12mL ethylene glycol were added to a 20mL glass vial and vigorously stirred (500 rpm) for 0.5h and sonicated for 0.5h to give a clear tan solution. And then sealing the glass bottle, heating the glass bottle in an oil bath kettle at 160 ℃ for 5 hours, naturally cooling, washing the product once with water and ethanol in sequence, centrifugally collecting, and drying the product in an oven at 60 ℃ for 12 hours to obtain Ir/CB.
TEM (Transmission Electron microscope) measurement and particle size measurement of Ir/CB as shown in FIG. 13 revealed that the metal particles were uniformly distributed on the carbon black and no agglomeration was found. As shown in FIG. 14, the average particle diameter of the Ir/CB particles is 1.1 nm.
X-ray powder diffraction (XRD) analysis (using a SmartLab instrument of Japan) was carried out on Ir/CB, IrCd/CB, IrGa/CB, IrSn/CB, IrZn/CB, and Irin/CB obtained in the above-mentioned examples 1 to 5 and comparative example 1, and as shown in FIG. 15, XRD of all samples had no distinct metal peak, demonstrating that the particle size was small.
Ir mass percent and Ir/M molar ratio statistics are carried out on Ir/CB, IrCd/CB, IrGa/CB, IrSn/CB, IrZn/CB and Irin/CB obtained in the above examples 1-5 and comparative example 1. As can be seen from Table 1, the non-noble metal content is relatively low, demonstrating that the non-noble metal is more difficult to reduce, while the overall Ir content is close.
TABLE 1 Ir mass percent and Ir to M molar ratio for various heterogeneous catalysts
Experimental example 1 Selective catalytic hydrogenation Activity and Selective analysis
A typical α, β -unsaturated aldehyde, cinnamaldehyde, was chosen as the catalytic substrate, and the catalytic activity and product selectivity of different catalysts (IrM/CB heterogeneous catalyst and Ir/CB for examples 1-5) were compared. The reaction mechanism is shown in the hydrogenation schematic diagram of cinnamaldehyde in fig. 16, cinnamaldehyde is firstly hydrogenated into cinnamyl alcohol, hydrogenated cinnamaldehyde and phenylpropyl alcohol under the action of a catalyst and hydrogen, and the ideal product is cinnamyl alcohol.
The heterogeneous catalytic hydrogenation reaction conditions are as follows: the adding amount of the catalyst is 3mg, the adding amount of the cinnamaldehyde is 50 mu L, the cinnamaldehyde and the cinnamaldehyde are added into a mixed solution of 1mL of water and 1mL of isopropanol, ultrasonic treatment is carried out for 10min to obtain a uniform mixed solution, the mixed solution is transferred into a liner of a 20mL high-pressure reaction kettle, hydrogen is introduced to 1MPa, most of gas is discharged, ventilation and gas release are carried out for 5 times, the final hydrogen pressure is set to 1MPa, the mixture is stirred for 11 hours at room temperature (IrGa/CB takes data of 10 hours of reaction), samples are taken every 2 hours, and the catalytic result is tested by a gas chromatography-mass spectrometer (GC-MS).
As can be seen from Table 2 and FIG. 17, most of the bimetallic catalysts (IrCd/CB, IrGa/CB, IrSn/CB, IrZn/CB, and Irin/CB) have better catalytic activity and product selectivity than single metal Ir/CB, which proves that doping of non-noble metal is beneficial to improving the catalytic hydrogenation capability; among them, IrCd/CB and IrGa/CB catalysts show good hydrogenation effects. As shown in fig. 18, the conversion rate and selectivity of IrCd/CB to cinnamaldehyde hydrogenation reaction with time gradually increase with the extension of reaction time, the selectivity of cinnamyl alcohol is basically maintained at above 90%, after 11 hours of reaction, the conversion rate of cinnamyl aldehyde reaches 99.8%, the selectivity of cinnamyl alcohol is 94.1%, and the performance is excellent. As shown in fig. 19, the conversion and selectivity of IrGa/CB to cinnamaldehyde hydrogenation reaction over time gradually increased with the increase of reaction time, and after 10 hours of reaction, the conversion of cinnamaldehyde was 98.0%, the selectivity of cinnamyl alcohol was 93.2%, and the performance was excellent.
Therefore, the IrCd/CB and the IrGa/CB prepared by adding the proper non-noble metal salt have better catalytic activity and product selectivity than those of the single-metal catalyst Ir/CB. After the reaction is carried out for 11 hours, the hydrogenation conversion rates of IrCd/CB and IrGa/CB catalyzed cinnamaldehyde are both greater than 93%, cinnamyl alcohol with the selectivity greater than 90% can be generated, the cinnamyl alcohol selectivity under the catalysis of Ir/CB is only 77.3%, and the result proves that the product selectivity can be greatly improved after Cd and Ga salt are added to form IrCd and IrGa alloy. After TOF is converted according to the Ir content, TOF of most of alloys is higher than that of pure Ir/CB, and the fact that the catalytic activity of the characterization of various alloys is higher is proved. In addition, as shown in fig. 20, after 4 times of recycling, the IrCd/CB catalyst still maintains excellent catalytic performance, and neither the substrate conversion rate nor the cinnamyl alcohol selectivity is significantly reduced. Further illustrates that the IrCd/CB obtained by the invention is an excellent alpha, beta-unsaturated aldehyde selective hydrogenation catalyst.
Further, X-ray photoelectron spectroscopy (XPS) analysis of the IrCd/CB catalyst shows that (as shown in FIG. 21), the electron binding energy of Ir is reduced after doping Cd (the XPS spectrogram of FIG. 22 shows the existence of Cd), and the electron of Cd is proved to be transferred to Ir, so that the Ir with negative electricity is more beneficial to adsorbing aldehyde groups with positive electricity on cinnamaldehyde, and the catalytic activity of IrCd/CB and the selectivity of cinnamyl alcohol are improved.
TABLE 2 conversion of cinnamaldehyde and selectivity of various products after 11h reaction over various heterogeneous catalysts
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (5)
1. The application of the carbon-supported Ir-based alloy catalyst in the selective hydrogenation reaction of alpha, beta-unsaturated aldehyde is characterized in that the preparation method of the carbon-supported Ir-based alloy catalyst comprises the following steps: IrCl is added to ethylene glycol3·xH2O, metal precursor salt, citric acid and carbon black, and stirring at room temperature and performing ultrasonic treatment to obtain a clear brown yellow solution; then, the brown yellow solution is placed at 160-180 ℃ under a sealed state for heating reaction for 5-6 hours, the solution is naturally cooled and then is washed and centrifugally collected to obtain the metal precursor salt CdCl2、Ga(acac)3、InCl3、ZnCl2、SnCl4·5H2One of O; the IrCl3·xH2The dosage proportion of O, metal precursor salt, citric acid, carbon black and glycol is as follows:
IrCl3·xH20.05 to 0.1mmol of O, 0.025 to 1mmol of metal precursor salt, 96 to 192mg of citric acid, 50 to 100mg of carbon black, and 12 to 18mL of ethylene glycol.
2. The use of the carbon-supported Ir-based alloy catalyst as set forth in claim 1 in the selective hydrogenation of α, β -unsaturated aldehydes, wherein the metal precursor salt is CdCl2Or Ga (acac)3。
3. The use of the carbon-supported Ir-based alloy catalyst according to claim 1 for the selective hydrogenation of α, β -unsaturated aldehydes, wherein the reaction temperature is 160 ℃ and the reaction time is 5 hours.
4. The application of the carbon-supported Ir-based alloy catalyst in the selective hydrogenation reaction of alpha, beta-unsaturated aldehyde as claimed in claim 1, wherein the room temperature is 20-30 ℃, the stirring speed is 400-600rpm, and the stirring and ultrasonic time is 0.5-1 h.
5. The use of the carbon-supported Ir-based alloy catalyst as set forth in claim 1 for the selective hydrogenation of α, β -unsaturated aldehydes, wherein the α, β -unsaturated aldehyde is cinnamaldehyde.
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