CN112973707A - NiSn/C core-shell composite nano-catalyst and preparation method and application thereof - Google Patents
NiSn/C core-shell composite nano-catalyst and preparation method and application thereof Download PDFInfo
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- 229910005887 NiSn Inorganic materials 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 47
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000003839 salts Chemical class 0.000 claims abstract description 42
- 229910001868 water Inorganic materials 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 22
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 22
- 230000008020 evaporation Effects 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 150000001298 alcohols Chemical class 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- -1 small molecule alcohols Chemical class 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 69
- 239000003054 catalyst Substances 0.000 abstract description 30
- 239000002243 precursor Substances 0.000 abstract description 25
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 30
- 239000002184 metal Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012018 catalyst precursor Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229910005102 Ni3Sn Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
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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
- B01J23/835—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 germanium, tin or lead
-
- B01J35/40—
-
- B01J35/615—
-
- 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
- C07C29/32—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 without formation of -OH groups
- C07C29/34—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 without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The application belongs to the technical field of catalysts. The application provides a NiSn/C core-shell composite nano catalyst, and a preparation method and application thereof. Adding Ni salt, Sn salt and a carbon source into deionized water, stirring to form a homogeneous sol solution, stirring and evaporating the sol solution to form gel, and drying and calcining to obtain the NiSn/C core-shell composite nano-catalyst. The carbon source is selected from polycarboxylic citric acid, can be used as a carbon source precursor and a reducing agent, a hydrophobic carbon shell layer can be constructed on the surface of NiSn bimetal, and a core-shell structure with a large specific surface area and a complete spherical shape can be obtained, so that the thermal stability of the active particles of the catalyst in a hydrothermal environment is improved, the agglomeration phenomenon is avoided, and the catalytic efficiency of ethanol coupling synthesis of high alcohol in a water phase is improved. The NiSn/C core-shell-shaped composite nano-catalyst is a heterogeneous catalyst, is easy to separate and recover, has small pollution and can be recycled after being recovered in the process of catalyzing ethanol to synthesize higher alcohol.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a NiSn/C core-shell composite nano catalyst, and a preparation method and application thereof.
Background
The C4+ alcohol can be used as a new generation of biofuel, has the specific advantages of high calorific value, easiness in mixing, high octane number, good hydrophobicity, easiness in separating, easiness in passivating, no corrosion to engine pipelines and the like, and is considered to be a clean mixed fuel with great potential. In general, the carbon chain extension can be achieved by condensation of small alcohols to produce higher alcohols, known as Guerbet condensation reactions. In 1899, Marcel Guerbet found that potassium hydroxide was used as a catalyst to make low molecular alcohol undergo aldol condensation to form branched isomeric higher alcohol at the beta position of hydroxyl group. The Guerbet condensation reaction provides a method for synthesizing isomeric higher alcohol by direct carbon-carbon coupling of micromolecule alcohol, generally, the Guerbet condensation reaction mechanism is that alcohol serving as a reaction raw material is dehydrogenated to generate aldehyde under the action of a catalyst, then nucleophilic addition aldol condensation is carried out, a molecule of water is removed to obtain unsaturated ketene, and finally selective hydrogenation is carried out under the action of the catalyst to obtain a product. The obtained higher alcohols are mostly isomeric alcohols containing branched chains, and the dehydrogenation of the alcohols to generate corresponding aldehydes is considered to occur under the catalytic action of metals, while general dehydrogenation metal catalysts also have catalytic hydrogenation capacity, so the catalytic systems of the carbon-carbon coupling reaction of the small molecular alcohols are generally dehydrogenation-hydrogenation catalysts and basic catalysts.
At present, the active metal of the dehydrogenation-hydrogenation catalyst mostly adopts organic metal, transition noble metal such as Pt, Pd, Ir and the like, and the aldol condensation mostly adopts homogeneous base such as NaOH, KOH and the like or solid base catalyst such as MgAl hydrotalcite, HAP and the like. Although the organic metal and noble metal catalysts show good catalytic activity, the organic metal and noble metal catalysts have the problems of high price, high recovery cost, unstable performance in a hydrothermal environment, difficulty in separation and environmental pollution, so that the condensation of biomass micromolecule alcohol to prepare higher alcohol fuel lacks application prospects.
Disclosure of Invention
In view of the above, the application provides a NiSn/C core-shell composite nano catalyst, and a preparation method and an application thereof, which can effectively improve the catalytic efficiency and catalytic stability of a dehydrogenation-hydrogenation catalyst, and can be used for catalyzing an ethanol aqueous solution to directly synthesize a higher alcohol fuel chemical.
The specific technical scheme of the application is as follows:
the first aspect of the application provides a preparation method of a NiSn/C core-shell composite nano catalyst, which comprises the following steps:
s1: adding Ni salt, Sn salt and a carbon source into deionized water, and stirring to form a homogeneous sol solution;
s2: stirring and evaporating the sol solution to form gel, and then drying and calcining to obtain the NiSn/C core-shell composite nano-catalyst;
the carbon source is selected from C6H8O7·H2O or C6H8O7。
In the application, metal Ni is used as a non-noble metal element, the yield of the metal Ni in the earth crust is rich, and the metal Ni is one of the best noble metal substitute materials. The electronic environment of the metal Ni can be changed by modifying Ni with the metal Sn, so that the metallicity of the metal Ni is regulated and controlled, methanation of the metal Ni is weakened in the dehydrogenation process of the micromolecular alcohol, and generation of higher alcohol is facilitated. The carbon source is selected from polycarboxylic citric acid, can be used as a carbon source precursor and a reducing agent, a hydrophobic carbon shell layer can be constructed on the surface of NiSn bimetal, and a core-shell structure with a large specific surface area and a complete spherical shape can be obtained, so that the thermal stability of the active particles of the catalyst in a hydrothermal environment is improved, the agglomeration phenomenon is avoided, and the catalytic efficiency of ethanol coupling synthesis of high alcohol in a water phase is improved.
Preferably, the Ni salt is selected from nickel nitrate, nickel chloride or nickel sulfate, and the Sn salt is selected from SnCl2·2H2O or SnCl4·5H2O。
Preferably, the molar ratio of the mixture of the Ni salt and the Sn salt to the carbon source is 1: (0.2-5). More preferably, the molar ratio of the mixture of the Ni salt and the Sn salt to the carbon source is 1: 1 or 1: 2.
preferably, the mass ratio of the Ni salt, the Sn salt, the carbon source, and the deionized water is 1.84: 0.11: (0.28-7): 5. more preferably, the mass ratio of the Ni salt, the Sn salt, the carbon source, and the deionized water is 1.84: 0.11: 2.8: 5.
preferably, the evaporation temperature in S2 is 80-120 ℃, the drying temperature is 80-120 ℃, and the calcination temperature is 300-800 ℃.
More preferably, the drying temperature in S2 is 100 ℃, the calcining temperature is 500 ℃, and the calcining is performed in a nitrogen atmosphere.
Preferably, the rotation speed of the stirring in S1 and S2 is 200-600 rpm.
The second aspect of the application provides a NiSn/C core-shell composite nano-catalyst prepared by the preparation method.
In the application, the prepared NiSn/C core-shell-shaped composite nano-catalyst is a heterogeneous catalyst, is easy to separate and recover, has little pollution and can be recycled after being recovered in the process of catalyzing ethanol to synthesize higher alcohol.
Preferably, the specific surface area of the NiSn/C core-shell composite nano-catalyst is 103.8-181.9m2(iv)/g, average particle diameter of 6.4-8.8 nm.
The third aspect of the application provides an application of the NiSn/C core-shell composite nano-catalyst in catalyzing small molecular alcohol to synthesize higher alcohol in a water phase.
In the application, the NiSn/C core-shell composite nano catalyst is used for catalyzing a small molecular alcohol aqueous solution to perform carbon-carbon coupling, so that higher alcohol can be directly prepared, the reaction condition is mild and pollution-free, spontaneous phase separation can be realized, and the conversion efficiency is greatly improved.
Preferably, the conditions for catalyzing the aqueous phase synthesis of the higher alcohol from the small molecular alcohol are as follows:
the NiSn/C core-shell composite nano-catalyst comprises the following components in percentage by weight: alkali: small molecule alcohol: the mass ratio of water is 0.1: 0.1: 3: 3;
the temperature of the catalysis is 200-270 ℃, the pressure is 0.1MPa, and the time is 24 h.
In summary, the application provides a NiSn/C core-shell composite nano-catalyst, and a preparation method and application thereof. Adding Ni salt, Sn salt and a carbon source into deionized water, stirring to form a homogeneous sol solution, stirring and evaporating the sol solution to form gel, and drying and calcining to obtain the NiSn/C core-shell composite nano-catalyst. The carbon source is selected from polycarboxylic citric acid, can be used as a carbon source precursor and a reducing agent, a hydrophobic carbon shell layer can be constructed on the surface of NiSn bimetal, and a core-shell structure with a large specific surface area and a complete spherical shape can be obtained, so that the thermal stability of the active particles of the catalyst in a hydrothermal environment is improved, the agglomeration phenomenon is avoided, and the catalytic efficiency of ethanol coupling synthesis of high alcohol in a water phase is improved. The NiSn/C core-shell-shaped composite nano-catalyst is a heterogeneous catalyst, is easy to separate and recover, has small pollution and can be recycled after being recovered in the process of catalyzing ethanol to synthesize higher alcohol.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is an SEM photograph of a product obtained in example 5 of the present application;
FIG. 2 is a TEM image of the product obtained in example 5 of the present application at different magnifications;
FIG. 3 is an SEM photograph of a product obtained in example 7 of the present application;
FIG. 4 is an SEM image of a product obtained in comparative example 1 of the present application;
FIG. 5 is an SEM image of a product obtained in comparative example 2 of the present application;
FIG. 6 is an XRD pattern of the product obtained in examples 1 to 7 (except for example 6) of the present application;
figure 7 is the bookApplication of N to the products obtained in example 1, example 3, example 5, examples 7 to 8 and comparative examples 1 to 22Physical adsorption (BET) diagram.
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 0.28: 5, i.e. the molar ratio of metal precursor (mixture of Ni and Sn salts) to citric acid is 5: 1;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Example 2
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 0.47: 5, i.e. the molar ratio of metal precursor (mixture of Ni and Sn salts) to citric acid is 3: 1;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Example 3
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 0.70: 5, i.e. the molar ratio of metal precursor (mixture of Ni and Sn salts) to citric acid is 2: 1;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Example 4
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 1.40: 5, namely the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 1;
(2) putting the sol solution obtained in the step (1) at 100 DEG CEvaporating on a magnetic stirrer to form gel, transferring the gel obtained by evaporation into a drying oven at 100 ℃ for drying for 48h to obtain the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Example 5
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 2.8: 5, namely the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 2;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
An SEM image of the product obtained in example 5 of the present application is shown in FIG. 1, and a TEM image of the product obtained in example 5 of the present application at different magnifications is shown in FIG. 2. The SEM image shows that the prepared catalyst is in a complete spherical core-shell structure, metal particles are wrapped by carbon, the particle size is uniformly dispersed, and the diameter of the particles is small.
Example 6
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 4.2: 5, i.e. metal precursors (mixture of Ni and Sn salts) and citratesThe molar ratio of the citric acid is 1: 3;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Example 7
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 7.0: 5, namely the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 5;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 500 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
The SEM image of the product obtained in example 7 of the present application is shown in fig. 3, which shows that the morphology of the obtained catalyst is uniform irregular cluster particles, and the particles on the cluster surface are rough, indicating that the interior is formed by aggregating secondary nanoparticles.
Example 8
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84:0.11: 2.8: 5, namely the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 2;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 600 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
Comparative example 1
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 2.8: 5, namely the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 2;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining the mixture for 4 hours at the temperature of 300 ℃ to obtain the NiSn/C core-shell composite nano catalyst.
The SEM image of the product obtained in comparative example 1 of the present application is shown in FIG. 4, in which it can be seen that the catalyst obtained was in the form of a lump and had a relatively random arrangement.
Comparative example 2
(1) A certain amount of Ni (NO)3)2·6H2O、SnCl4·5H2O and C6H8O7·H2O is synchronously added into deionized water and stirred to form homogeneous sol, wherein the mass ratio of each substance is Ni (NO)3)2·6H2O：SnCl4·5H2O：C6H8O7·H2O: water 1.84: 0.11: 2.8: 5, i.e. metal precursor (N)Mixture of i salt and Sn salt) to citric acid in a molar ratio of 1: 2;
(2) and (2) putting the sol solution obtained in the step (1) on a magnetic stirrer at 100 ℃ for evaporation to form gel, transferring the gel obtained by evaporation to a drying oven at 100 ℃ for drying for 48h, and obtaining the precursor of the NiSn composite nano-catalyst. Then putting the catalyst precursor in N2Calcining at 800 ℃ for 4h to obtain the NiSn/C core-shell composite nano-catalyst.
The SEM image of the product prepared in comparative example 2 of the application is shown in FIG. 5, and the SEM image shows that the prepared catalyst has large particle size, is easy to aggregate, has poor dispersity and is easy to deactivate in the reaction.
The XRD patterns of the products obtained in examples 1-7 (except for example 6) of the present application are shown in FIG. 6. As is clear from the figure, as the amount of citric acid added increases, Ni and Ni as metals gradually appear3Crystal form of Sn, Ni3Sn plays a decisive role in the catalytic process, which shows that citric acid is used as a carbon shell layer of a carbon source to be beneficial to realizing the stability of a metal center; however, when the amount of citric acid added was increased, Ni was added3The crystalline phase of Sn slowly weakens until it disappears.
N of the products obtained in examples 1, 3, 5 and 7 of the present application2The physical adsorption (BET) patterns are shown in FIGS. 7(a) and 7(b), and N of the products obtained in examples 5 and 8 and comparative examples 1 to 2 of the present application2The physical adsorption (BET) patterns are shown in FIG. 7(c) and FIG. 7 (d). FIGS. 7(a) and 7(b) show that the products obtained in examples 1 and 3, in which the amount of citric acid added was small, had a broad particle size distribution and non-uniform particle size; the particle size of the product obtained in example 7 in which the amount of citric acid added was large, and clustering was likely to occur. FIG. 7(c) shows that the products prepared using different carbonization temperatures have significant differences in performance with the same amount of carbon source. The isothermal hysteresis loops corresponding to the prepared catalyst at the carbonization temperatures of 500, 600 and 800 ℃ are typical H1 type, which shows relatively narrow pore size distribution and uniform particle size; the isothermal hysteresis loop corresponding to the carbonization temperature of 300 ℃ is typical H2 type, which shows that the pore size distribution and the pore shape of the catalyst are not uniform. The results of the pore size distribution in FIG. 7(d) are also in connection with the above analysisIt is true that the pore size distribution is narrower at carbonization temperatures of 500, 600 and 800 c, with an average pore size around 7nm, wherein 500 c corresponds to a larger pore size distribution of the catalyst than 800 c, for reasons which may be related to the pore structure formed by decomposition and carbonization of citric acid.
Example 8
And (3) carrying out a reaction of the product prepared in the examples 1-7 and the comparative examples 1-2 and a homogeneous alkali (NaOH) in a 50ml steel mechanical stirring reaction kettle to synergistically catalyze the carbon-carbon coupling of ethanol to synthesize the higher fuel alcohol, wherein the NiSn/C core-shell composite nano catalyst: NaOH: ethanol: the mass ratio of water is 0.1: 0.1: 3: 3, the reaction temperature is 250 ℃, the initial pressure is 0.1MPa, the reaction time is 24 hours, after the reaction is finished, the reaction kettle is cooled to room temperature, centrifugation and filtration are carried out, a liquid phase and a catalyst solid phase are obtained, gas phase and liquid phase products are collected, the liquid phase products are centrifuged and then stand to accelerate spontaneous phase layering to obtain an organic phase and a water phase, after the liquid phase products are centrifugally separated, detection and analysis are carried out through gas chromatography, the main products of the organic phase are C4+ higher alcohols, and the catalytic activity results of the products prepared in examples 1-7 and comparative examples 1-2 are shown in the following table 1.
Table 1 shows that, in the preparation process, as the amount of the citric acid precursor increases, the effect of catalytically synthesizing higher alcohol tends to increase first and then decrease. The thickness of the carbon shell layer coated on the surface of the NiSn metal particle is related, and the proper thickness of the carbon shell layer is beneficial to protecting the metal core of the catalyst and enhancing the catalytic stability of the catalyst in a hydrothermal reaction environment, so that the conversion rate of ethanol and the selectivity of organic phase generation are improved. When the amount of the carbon precursor is continuously increased, the thickness of the carbon shell layer is continuously increased, the substance transfer of the aqueous phase and the catalyst metal active core in the reaction is not facilitated, and the conversion rate of the ethanol is reduced. Meanwhile, the uneven pore size distribution and the uneven pore shape of the catalyst can be caused by the excessively low carbonization temperature, and the particle aggregation is easily caused by the excessively high carbonization temperature, so that the catalytic activity of the catalyst is influenced.
TABLE 1 results of catalytic activity of products obtained in examples 1-7 and comparative examples 1-2
The above experimental results show that less citric acid adopted in the preparation process can cause aggregation and agglomeration of metal particles, uneven particle distribution, loss of the significance of protecting metal cores and enhancing catalytic stability, while more citric acid can cause carbon shell clusters and be unfavorable for mass transfer between a water phase and metal active cores, and when the molar ratio of the metal precursor (mixture of Ni salt and Sn salt) to the citric acid is 1: 1 or 1: 2, it is advantageous to form uniformly distributed spherical NiSn/C particles. In addition, the NiSn/C core-shell composite nano-catalyst prepared at the calcining temperature of 500 ℃ has better catalytic activity. The catalyst prepared by the method can be used for catalyzing ethanol to synthesize C4+ higher alcohol, the highest ethanol conversion rate reaches 58.3%, and the selectivity of C4+ higher alcohol reaches 92.1%.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. A preparation method of a NiSn/C core-shell composite nano catalyst is characterized by comprising the following steps:
s1: adding Ni salt, Sn salt and a carbon source into deionized water, and stirring to form a homogeneous sol solution;
s2: stirring and evaporating the sol solution to form gel, and then drying and calcining to obtain the NiSn/C core-shell composite nano-catalyst;
the carbon source is selected from C6H8O7·H2O or C6H8O7。
2. The method of claim 1Method, characterized in that the Ni salt is selected from nickel nitrate, nickel chloride or nickel sulphate, the Sn salt is selected from SnCl2·2H2O or SnCl4·5H2O。
3. The method according to claim 1, wherein the molar ratio of the mixture of the Ni salt and the Sn salt to the carbon source is 1: (0.2-5).
4. The method according to claim 1, wherein the mass ratio of the Ni salt, the Sn salt, the carbon source, and the deionized water is 1.84: 0.11: (0.28-7): 5.
5. the method as claimed in claim 1, wherein the evaporation temperature in S2 is 80-120 ℃, the drying temperature is 80-120 ℃, and the calcination temperature is 300-800 ℃.
6. The method as claimed in claim 1, wherein the rotation speed of the stirring in S1 and S2 is 200-600 rpm.
7. A NiSn/C core-shell composite nano-catalyst is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. The NiSn/C core-shell composite nanocatalyst of claim 7, wherein the NiSn/C core-shell composite nanocatalyst has a specific surface area of 103.8-181.9m2(iv)/g, average particle diameter of 6.4-8.8 nm.
9. The use of the NiSn/C core-shell composite nano-catalyst of claim 7 in catalyzing small molecular alcohols to synthesize higher alcohols in aqueous phase.
10. The use according to claim 9, wherein the conditions for catalyzing the aqueous phase synthesis of higher alcohols from small molecule alcohols are as follows:
the NiSn/C core-shell composite nano-catalyst comprises the following components in percentage by weight: alkali: small molecule alcohol: the mass ratio of water is 0.1: 0.1: 3: 3;
the temperature of the catalysis is 200-270 ℃, the pressure is 0.1MPa, and the time is 24 h.
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