CN117399012A - Catalyst for packaging rare alloy nano particles and preparation method and application thereof - Google Patents

Catalyst for packaging rare alloy nano particles and preparation method and application thereof Download PDF

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CN117399012A
CN117399012A CN202311349195.6A CN202311349195A CN117399012A CN 117399012 A CN117399012 A CN 117399012A CN 202311349195 A CN202311349195 A CN 202311349195A CN 117399012 A CN117399012 A CN 117399012A
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catalyst
metal
oxygen
nano particles
alloy nano
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杨世和
洪梅
袁海丰
高金强
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract

The invention belongs to the technical field of catalysts, and discloses a catalyst for packaging rare alloy nano particles, a preparation method and application thereof. The catalyst takes oxygen doped porous carbon as a carrier, and dilute alloy nano particles are encapsulated in the carrier, wherein the dilute alloy nano particles comprise M metal and base metal Cu; m metal is selected from at least one of Ni, co, zn, fe, V, ti; the content of M metal in the catalyst is 0.5-3.0wt%. The catalyst disclosed by the invention relates to a simple synthesis strategy, and trace M metal doping in MCu dilute alloy induces an atomic-level metal M-Cu synergistic effect and an enhanced Schottky junction, so that cost-effective multi-catalyst synthesis is universal. The catalyst can be effectively and selectively hydrogenated and reduced in a wide catalytic range under mild water conditions, is environment-friendly and has excellent stability, and has great industrial application prospect.

Description

Catalyst for packaging rare alloy nano particles and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst for packaging rare alloy nano particles, a preparation method and application thereof.
Background
A thin alloy (dilutealloy) refers to an assembled material formed by adding a small amount of a heterogeneous monodisperse metal to a given host element. Smart methods to enhance the synergistic effect of structure and electrons include the preparation of dilute bimetallic alloy clusters or Nanoparticles (NPs), the use of the Mott-Schottky effect, and functional doping of the support. Limiting isolated metal atoms or clusters in the crystalline porous material can further overcome the shortcomings of conventional heterogeneous catalysis, thereby obtaining a sinter resistant catalyst with improved activity and selectivity.
In Transition Metal (TM), noble metals are dominant due to their high reactivity and functional group tolerance in various reactions. However, the high cost of noble metals and their tendency to aggregate under severe reaction conditions limit their use. The monoatomic catalysts (single atom catalysts, SAC) and monoatomic alloys (single atom alloys, SAA) have maximized atom utilization efficiency, minimizing the use of precious metals, while exhibiting exceptional catalytic activity. In recent years, scholars at home and abroad have explored combinations of various metals with a few noble metals, including PdCo, auCo, ptCu and PtFe, which significantly reduce the use of noble metal Pd. Such as: the ultra-thin alloy (ultra dilute alloy, UDA) reported in document 1 (Applied Catalysis B: environmental 2021,284,119737) is formed by dispersing Pt atom couples on bulk Cu nanoparticles to replace Cu atoms. The catalyst is subjected to furfural hydrogenation reaction under the hydrogen pressure of 1.0-2.0MPa, and shows catalytic performance superior to that of a bimetallic nanoparticle alloy catalyst with pure Cu or other components. Document 2 (Nature Catalysis 2022,5, 503-512) developed a highly active oxygen reduction catalyst, i.e., a composite Pt-based nanoparticle and a carbon-based non-noble metal carrier, to form a completely new composite catalyst (Pt-Fe-N-C). In the constant voltage test, pt-Fe-N-C showed excellent current stability in both oxygen and air environments, with little decrease in platinum mass activity after 100000 cycles of testing. Supporting dilute noble metal-based alloys on porous substrates has made an important step toward industrial applications for composite catalysts. At present, the carrier materials of the dilute alloy are mainly metal oxides, which can promote mass transfer and strengthen the stability of metals.
Document 3 (chem. Eng. J.,2018,351,995-1005) reports a pd—ag alloy catalyst supported on MCM-41. Due to the synergistic effect between the two metals, the incorporation of Ag into the Pd-based catalyst significantly increases its catalytic activity and selectivity to Cinnamaldehyde (CAL) hydrogenation to benzene propanal (HCAL) compared to a catalyst without Ag. However, a large amount of noble metal is consumed for preparing such a catalyst, and thus the preparation method lacks versatility.
Chinese patent CN107497488A discloses a preparation method and application of Au-Pd monoatomic alloy catalyst with high hydrogenation selectivity. According to the invention, MOF with amino linked with organic ligand is used as a carrier, and sodium borohydride direct reduction method is used for preparing the monoatomic alloy catalyst with Pd dispersed on the surface of Au, and excellent selectivity is shown in reductive amination reaction of nitro compound and aldehyde compound. However, the catalyst uses chloroauric acid and chloropalladate as metal precursors, so that scarce noble metal resources are greatly consumed, cyclohexane is used as a solvent in the catalytic process, and the concept of green chemistry is not met.
Chinese patent CN108620092a discloses an alumina supported PtCu monoatomic alloy catalyst, and preparation method and application thereof. According to the invention, the Pt/Cu monoatomic alloy loaded with alumina is prepared by a simple co-impregnation method by adopting an atomic dilution strategy, the dehydrogenation activity is very high in the reaction of preparing olefin by dehydrogenating low alkane, the propylene selectivity can reach more than 90%, the Pt consumption is small, the utilization rate is high, and compared with an industrial pure Pt-based catalyst, the catalyst has a low cost and a narrow application range.
Based on the above research situation, a more convenient method is sought to prepare the multifunctional catalyst with high performance and cost effectiveness, and the method has important significance in the selective catalytic reaction of various substrates under the condition of mild water phase.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. The invention provides a catalyst for packaging rare alloy nano particles, a preparation method and application thereof. The catalyst can completely take base metal as a main body to serve as an active component, and has very high activity, selectivity and stability for the transfer hydrogenation reaction of nitro compounds and the low-pressure selective hydrogenation of aldehyde compounds under a mild aqueous phase condition.
The invention utilizes the different solubility of carbon in M metal and base metal to embed and dilute M in ultrathin oxygen doped porous carbon (OC) carrier x Cu y (M is a metal element) alloy nanocrystals, a rechecked shell M can be obtained x Cu y @oc nanocatalyst. The catalyst can better utilize base metal as main active component, is a highly cost-effective catalyst, has very high activity and selectivity for the transfer hydrogenation reaction of nitro compounds and the low-pressure selective hydrogenation of aldehydes compounds under the condition of mild aqueous phase, andand due to the wrapping effect of the oxygen doped graphene carbon shell, the stability of the graphene carbon shell is greatly improved, and meanwhile, the material and electron transfer are not influenced.
Aiming at the problems of insufficient atomic efficiency, lower selectivity and large noble metal usage amount of the conventional multiphase transition metal catalyst, the invention adjusts the geometry and electronic structure of isolated few metal species by adjusting the interaction of trace transition metal M, main body base metal Cu and porous semiconductor carrier, thereby endowing high catalytic activity and reaction universality. The aim is to provide a multifunctional catalyst which can be used for transferring hydrogenation or low-pressure hydrogenation under mild water conditions with wide application range and high efficiency and is very cost-effective. The catalyst uses oxygen doped porous carbon (OC) as a carrier to load dilute alloy nano particles composed of trace transition metal M and main body base metal such as Cu. The catalyst has simple preparation process, is suitable for large-scale production, and can realize the efficient (conversion rate > 95.6%) directional (selectivity > 92.6%) conversion of various substrates into target products under the environment-friendly water-phase mild condition.
A first aspect of the invention provides a catalyst encapsulating dilute alloy nanoparticles.
A catalyst encapsulating a dilute alloy nanoparticle, the catalyst having oxygen doped porous carbon (OC) as a carrier, the dilute alloy nanoparticle being encapsulated in the carrier, the dilute alloy nanoparticle comprising an M metal and a base metal Cu;
the M metal is at least one selected from Ni, co, zn, fe, V, ti;
the content of the M metal in the catalyst is 0.5-3.0wt%.
In the catalyst disclosed by the invention, the content of M metal plays a very important role in the catalytic performance of the catalyst, and unexpected technical effects can be generated.
Preferably, the M metal may be further selected from at least one of Pd, ir and Rh.
Preferably, the content of M metal in the catalyst is 0.8-2.0wt%; further preferably, the M metal is present in an amount of 1.0 to 2.0wt%.
Preferably, the content of Cu in the catalyst is 56-58.5wt%; further preferably, the Cu content is 57.5-58wt%.
Preferably, the rare alloy nanoparticles consist of Ni and Cu.
Preferably, in the catalyst, cu content (or called loading) is 57.50-57.99wt%, and Ni content (or called loading) is 1.71-1.82wt%; further preferably, in the catalyst, the Cu content is 57.99wt% and the Ni content is 1.82wt%.
Preferably, oxygen doping in the support means that oxygen is present homogeneously in the grapheme-like carbon shell support in the form of hydroxyl oxygen (C-OH) or ether bond oxygen (O-C-O).
Preferably, the pores in the carrier are mainly mesopores (2-50 nm), and micropores and macropores are auxiliary.
In a second aspect, the invention provides a method of preparing a catalyst encapsulating dilute alloy nanoparticles.
A method for preparing a catalyst for encapsulating rare alloy nanoparticles, comprising the steps of:
1) Stirring and crystallizing a metal precursor, an oxygen-containing ligand, alkali and a solvent, and then separating to obtain a metal compound;
2) And (3) carrying out heat treatment on the metal compound obtained in the step (1) to obtain the catalyst.
Preferably, in step 1), the crystallization is carried out under stirring at room temperature.
Preferably, in step 1), the separation comprises centrifugation and vacuum drying.
Preferably, in step 1), the metal precursor is a mixture of an M metal salt and a copper salt.
Preferably, the M metal salt is selected from at least one of nickel nitrate, iron nitrate, cobalt nitrate, zinc nitrate, metavanadate, tetraethyl titanate, and hydrates thereof.
Preferably, the M metal salt may further include any one of palladium nitrate, palladium chloride, iridium dicarbonyl acetylacetonate, or rhodium dicarbonyl acetylacetonate.
Preferably, the copper salt is at least one of copper nitrate or a hydrate thereof.
Preferably, M metal salt, an oxygen-containing ligand, alkali and a solvent are mixed to obtain a solution A, then copper salt and the solvent are fused to obtain a solution B, nitrogen is introduced into the solution A, the solution A is stirred, then the solution B is dripped into the solution A to react for 4.0-6.0 hours at room temperature, the precipitate is obtained through centrifugation, the precipitate is washed for 3-10 times, and then the precipitate is dried in a vacuum furnace to obtain the metal compound. I.e. the M metal salt and copper salt are added in steps.
Preferably, in step 1), the oxygen-containing ligand is at least one selected from benzoic acid, terephthalic acid, trimesic acid, 2-amino-1, 3, 5-benzene tricarboxylic acid.
Preferably, in step 1), the base is selected from CH 4 N 2 O、NaOH、KOH、NH 3 ·H 2 O、Na 2 CO 3 At least one of them.
Preferably, in step 1), the solvent is at least one selected from ethanol, methanol, isopropanol, acetonitrile, and water.
The metal precursor, the oxygen-containing ligand and the alkali may be prepared into a solution before being stirred with the solvent for crystallization.
Preferably, in step 1), the duration of the stirring crystallization is 70-720min, preferably 90-720min.
Preferably, in step 2), the temperature of the heat treatment is 380-700 ℃, preferably 400-700 ℃.
Preferably, in step 2), the heat treatment is performed at a programmed temperature, and the temperature rising rate is 1-7deg.C/min, preferably 1-6deg.C/min.
Preferably, in step 2), the heat treatment is performed under a protective atmosphere.
Preferably, the protective atmosphere is at least one selected from nitrogen, argon or hydrogen-argon mixture.
A third aspect of the invention provides the use of a catalyst encapsulating dilute alloy nanoparticles.
The catalyst is applied to the transfer hydrogenation reaction of nitro compounds with hydrazine hydrate or sodium borohydride as a hydrogen source.
Preferably, the application comprises the following steps:
mixing a catalyst, a nitro compound, a reducing agent and deionized water under atmospheric pressure, then placing in an oil bath for heating reaction, and performing qualitative and quantitative analysis on a target product and the yield thereof by a Gas Chromatograph (GC), a gas chromatograph-mass spectrometer (GC-MS) and an ultraviolet-visible spectrophotometer (UV-2550) at intervals; the reducing agent is any one of hydrazine hydrate, formic acid, potassium formate and sodium borohydride.
Preferably, the molar ratio of substrate to active component in the catalyst during the heating reaction is (150-1050): 1.
Preferably, the deionized water is used in an amount of 5-15mL.
Preferably, the oil bath temperature is 25-60 ℃.
The catalyst is in H 2 Use in the directional hydrogenation of aldehydes which act as a source of hydrogen.
Preferably, the application comprises the following steps:
deionized water is used as a reaction solvent and added into a high-pressure reaction kettle, a certain amount of substrate and catalyst are added, the preferred molar ratio of the substrate to the catalyst is (100-550): 1, and 0.2-1.5MPaH is filled into the high-pressure reaction kettle 2 The reaction system is stirred for 90-360min at 25-100 ℃, after the reaction system is cooled to room temperature, the catalyst is centrifugally separated, and the reaction solution is analyzed by GC and GC-MS.
The conversion rate of the substrate is over 95.6 percent, and the selectivity of the target product is over 92.6 percent.
The catalyst disclosed by the invention is wide in catalytic range, is widely applicable to hydrogenation reactions of various nitro compounds and aldehyde compounds, and has excellent catalytic activity, high target product selectivity and good stability.
Compared with the prior art, the invention has the following beneficial effects:
1) The catalyst takes the precursor of which the transition metal salt is taken as an active component and the oxygen doped graded porous carbon generated in situ through heat treatment as a carrier, and the preparation process only involves conventional pretreatment steps such as one-pot stirring crystallization, centrifugation, drying, heat treatment and the like, so that the high-efficiency catalyst rich in the rare alloy nano particles can be obtained, the process is extremely simple and convenient, and the catalyst is suitable for large-scale batch production.
2) The invention relates to a simple synthesis strategy, and trace M metal doping in MCu dilute alloy induces an atomic-level metal M-Cu synergistic effect and an enhanced Schottky junction, so that the synthesis of a cost-effective multifunctional catalyst is universal. The MCu@OC can be subjected to selective hydrogenation reduction in a wide effective catalytic range under mild aqueous conditions, is environment-friendly and has excellent stability, and has great industrial application prospect.
3) The catalyst has excellent catalytic performance, can reduce high conversion rate (more than 97%, such as 97.9%) and high yield (more than 97%, such as 97.3%) of p-chloronitrobenzene into p-chloroaniline in water at normal pressure and normal temperature under environment-friendly conditions, has good stability, can be recycled for more than 11 times, such as 12 times, has no obvious reduction of catalytic performance, has extremely high industrial value, and has important application significance.
4) The catalyst provided by the invention has good substrate universality. When the substrate is any one of various nitro compounds and aldehyde compounds, the catalyst also exhibits excellent catalytic activity and high yield of the target product.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the catalysts prepared in examples 1-6;
FIG. 2 is a Raman scattering (Raman) chart of the catalysts prepared in examples 1-3 and example 5;
FIG. 3 shows N of the catalysts prepared in examples 1 to 3 and example 5 2 Adsorption-desorption isotherms and pore size distribution curves;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the catalyst prepared in example 1;
FIG. 5 is a schematic structural diagram of a carbon support with an oxygen-doped hierarchical pore structure in the catalyst prepared in example 1;
FIG. 6 is a graph showing the distribution of the particle diameters of a Transmission Electron Microscope (TEM), a high-resolution transmission electron microscope (HR-TEM), and a catalyst obtained in example 1 and example 5;
FIG. 7 is a line scan of the elements of the high angle annular dark field image (HAADF) and corresponding representative particles (NPs) of the catalysts prepared in examples 1 and 5, and the corresponding element map;
FIG. 8 is an in situ IR absorption diagram of the catalyst prepared in example 1 and example 5 with respect to CO molecules;
FIG. 9 is a graph of the ultraviolet visible diffuse reflectance spectrum (UV-vis DRS) of the catalyst prepared in examples 1-3, example 5;
FIG. 10 is an X-ray photoelectron spectrum (XPS) of the catalyst prepared in examples 1-3 and example 5;
FIG. 11 shows the Auger electron energy spectrum (CuL) of Cu for the catalyst obtained in example 1-2 3 VV) map;
FIG. 12 shows the relation of H between the catalysts prepared in examples 1 to 3 and example 5 2 Programmed temperature-rising reduction (H) 2 -TPR) map;
FIG. 13 shows the catalyst prepared in examples 1-2 with respect to H 2 Programmed temperature desorption (H) 2 -TPD) map;
FIG. 14 is a synchrotron radiation fine absorption spectrum (XAS) analysis of the catalyst prepared in example 1 with respect to the Cu K-absorption edge;
FIG. 15 is a synchrotron radiation fine absorption spectrum (XAS) analysis of the catalyst prepared in example 1 with respect to the Ni K-absorption edge;
FIG. 16 is a graph showing the comparison of the performance of the catalysts prepared in examples 1-3 and example 5 in the transfer hydrogenation of p-chloronitrobenzene;
FIG. 17 is a graph showing the recycling performance of the catalyst prepared in example 1 in the p-chloronitrobenzene transfer hydrogenation reaction;
FIG. 18 is a surface potential analysis of the catalyst prepared in example 1;
FIG. 19 is a graph showing the comparison of the performance of the catalyst prepared in examples 1-2 in the transfer hydrogenation of p-nitrophenol;
FIG. 20 is a graph showing the performance of the catalyst prepared in examples 1-2 in the hydrogenation of furfural.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1
A method for preparing a catalyst for encapsulating rare alloy nanoparticles, comprising the steps of:
1) 0.6mmol Ni (NO) 3 ) 2 ·6H 2 O was dissolved in 60mL of methanol and 100mL of ultrapure water, and a mixed solution of 50mmol of terephthalic acid and 23mmol of NaOH was added dropwise with stirring until the pH was approximately 10.83, which was referred to as solution A, and 12mmol of Cu (NO 3 ) 2 ·6H 2 O is dissolved in 60mL of methanol and 100mL of ultrapure water to form a solution B, then the solution B is slowly added into the solution A under nitrogen bubbling and continuous stirring, after the reaction is kept at room temperature for 360min, a precipitate is obtained through centrifugation, the precipitate is washed three times with water and methanol, and then the precipitate is completely dried in a vacuum furnace for one night to obtain a metal compound (also called as a nano composite material);
2) And (3) heating the metal compound obtained in the step (1) from room temperature to 550 ℃ at a speed of 5 ℃/min in a tubular furnace with an argon atmosphere, preserving heat for 120min, and naturally cooling to room temperature to obtain the catalyst.
The metal content in the catalyst was measured by inductively coupled plasma atomic emission spectrometry to obtain a catalyst having a Cu content (or referred to as loading) of 57.99wt% and a Ni content of 1.82wt%. The catalyst prepared in this example was labeled CuNi 0.05 Catalyst @ OC or # 1.
Example 2
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 The molar quantity of O is 0, and the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry, so that the Cu content in the catalyst is 58.62wt%. The catalyst prepared in this example was labeled as Cu/OC or 2# catalyst.
Example 3
Preparation was carried out by the method of example 1, with the difference that Cu (NO) in step 1) was used only 3 ) 2 ·6H 2 The molar amount of O is 0; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry, and the Ni content in the catalyst is 1.86wt%. The catalyst prepared in this example was labeled as Ni@OC or 3# catalyst.
Example 4
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 The molar amount of O was 3mmol; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry, and the Cu content in the catalyst is 55.89wt% and the Ni content in the catalyst is 0.39wt%. The catalyst prepared in this example was labeled CuNi 0.01 Catalyst @ OC or # 4.
Example 5
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 The molar amount of O was 3mmol; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry, and the Cu content in the catalyst is 58.93wt% and the Ni content in the catalyst is 8.52wt%. The catalyst prepared in this example was labeled CuNi 0.25 Catalyst @ OC or # 5.
Example 6
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 The molar amount of O was 7.8mmol; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry, and the Cu content in the catalyst is 59.21wt% and the Ni content is 11.91wt%. The catalyst prepared in this example was labeled CuNi 0.65 Catalyst @ OC or 6 #.
Example 7
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 O is replaced by Zn (NO) 3 ) 2 ·6H 2 O; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry.Thus obtaining the CuZn thin alloy catalyst.
Example 8
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 O is replaced by Fe (NO) 3 ) 2 ·9H 2 O; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry.
Example 9
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 O is replaced by Co (NO) 3 ) 2 ·6H 2 O; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry.
Example 10
Preparation was carried out by the method of example 1, with the difference that Ni (NO) in step 1) was used only 3 ) 2 ·6H 2 O is replaced by palladium nitrate solution; the metal content of the obtained catalyst is measured by inductively coupled plasma atomic emission spectrometry.
1. The catalyst structure is characterized as follows:
FIG. 1 is an X-ray diffraction (XRD) pattern of the catalysts prepared in examples 1-6.
FIG. 2 is a Raman scattering (Raman) chart of the catalysts prepared in examples 1-3 and example 5;
FIG. 3 shows N of the catalysts prepared in examples 1 to 3 and example 5 2 Adsorption-desorption isotherms and pore size distribution curves; as can be seen from FIG. 3, the catalyst pairs N prepared in the different examples 2 The adsorption-desorption effects are different, and the pore size distribution is also different. It can be seen that the amount of raw materials for preparing the catalyst is changed, so that the structure of the prepared catalyst is greatly changed.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the catalyst prepared in example 1;
FIG. 5 is a schematic structural diagram of a carbon support with an oxygen-doped hierarchical pore structure in the catalyst prepared in example 1; namely, the carrier can form a carbon cage structure and can play a role in packaging the rare alloy nano particles.
FIG. 6 is a schematic diagram of example 1 anda Transmission Electron Microscope (TEM), a high resolution transmission electron microscope (HR-TEM), and a particle size distribution diagram of the catalyst obtained in example 5; wherein, the diagrams a) and b) are CuNi respectively 0.05 A Transmission Electron Microscope (TEM) plot of OC and a particle size distribution plot of the corresponding particles (NPs); figures c), d) are CuNi 0.05 High resolution transmission electron microscope (HR-TEM) image of the @ OC. Fig. e), f) are respectively CuNi 0.25 A Transmission Electron Microscope (TEM) plot of OC and a particle size distribution plot of the corresponding particles (NPs); graph g), h) is CuNi 0.25 High resolution transmission electron microscope (HR-TEM) image of the @ OC.
FIG. 7 is a line scan of the elements of the high angle annular dark field image (HAADF) and corresponding representative particles (NPs) of the catalysts prepared in examples 1 and 5, and the corresponding element map; figures a) and b) are respectively CuNi 0.05 Element line scans of high angle annular dark field image (HAADF) of OC and corresponding representative particles (NPs), and graphs c), d), e), f) are corresponding element maps; g) H) are respectively CuNi 0.25 An elemental line scan of a high angle annular dark field image (HAADF) of OC and corresponding representative particles (NPs), and i), j), k), l) are the corresponding elemental maps.
FIG. 8 is an in situ IR absorption diagram of the catalyst prepared in example 1 and example 5 with respect to CO molecules; FIG. a) is CuNi 0.05 An in situ infrared adsorption experimental profile of OC for CO; FIG. b) is CuNi 0.25 In situ infrared adsorption experimental profile of OC with respect to CO. From this, it can be seen that the catalysts prepared in example 1 and example 5 are significantly different in the in-situ infrared adsorption effect with respect to CO molecules.
FIG. 9 is a graph of ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) of the catalysts prepared in examples 1-3 and example 5.
FIG. 10 is an X-ray photoelectron spectrum (XPS) of the catalyst prepared in examples 1-3 and example 5; wherein 1# represents CuNi 0.05 @OC, 2# represents Cu/OC, 3# represents Ni@OC, 5# represents CuNi 0.25 @OC)。
FIG. 11 shows the Auger electron energy spectrum (CuL) of Cu for the catalyst obtained in example 1-2 3 VV) map.
FIG. 12 shows the relation of H between the catalysts prepared in examples 1 to 3 and example 5 2 Programmed temperature-rising reduction (H) 2 -TPR) map.
FIG. 13 shows the catalyst prepared in examples 1-2 with respect to H 2 Programmed temperature desorption (H) 2 -TPD) map.
FIG. 14 is a synchrotron radiation fine absorption spectrum (XAS) analysis of the catalyst prepared in example 1 with respect to the Cu K-absorption edge; wherein, the graph a) is an X-ray absorption near-edge structure (XANES) spectrogram of a CuK-absorption edge; diagram b) is the first derivative corresponding to XANES; figure c) is an extended X-ray absorption fine structure (EXAFS) spectrum of the corresponding k-space; panel d) is the R-space analysis corresponding to the CuK-absorption edge.
FIG. 15 is a synchrotron radiation fine absorption spectrum (XAS) analysis of the catalyst prepared in example 1 with respect to the Ni K-absorption edge; wherein, the graph a) is an X-ray absorption near-edge structure (XANES) spectrogram of a Ni K-absorption edge; diagram b) is the first derivative corresponding to XANES; figure c) is an extended X-ray absorption fine structure (EXAFS) spectrum of the corresponding k-space; panel d) is an R-space analysis corresponding to the Ni K-absorption edge.
2. The catalytic effect was tested as follows:
in a 50mL round bottom flask containing 15mL of deionized water, 20mg of 1# 6 catalyst, 0.5mmol of p-chloronitrobenzene and 1.5mmol of hydrazine hydrate were added respectively, and reacted at 50℃for 240min, and the reactants and products were subjected to qualitative and quantitative analyses by GC and GC-MS, and the results are shown in Table 1.
The structural characteristics of the 1# -3# catalyst and the 5# catalyst are shown in Table 2.
The results of thermodynamic studies on the 1# -3# catalyst and the 5# catalyst are shown in Table 3.
Table 1:1# 6 catalyst for transferring hydrogenation performance of p-chloronitrobenzene
Sequence number Conversion (%) Selectivity (%)
2#(Cu/OC) 27.7 99.3
3#(Ni@OC) 40.2 87.1
4#(CuNi 0.01 @OC) 56.5 96.2
1#(CuNi 0.05 @OC) 97.9 99.4
5#(CuNi 0.25 @OC) 99.8 88.7
6#(CuNi 0.65 @OC) 73.2 81.3
As can be seen from table 1, the catalyst prepared in example 1 had the best catalytic effect, which was far superior to the catalytic effect of the catalysts prepared in other examples. Thus, it was found that the catalyst had unexpected technical effects when the Ni content in the catalyst was 1.82wt%.
FIG. 16 is a graph showing the comparison of the performance of the catalysts prepared in examples 1-3 and example 5 in the transfer hydrogenation of p-chloronitrobenzene; FIG. a) is a graph showing the performance of various catalysts for the transfer hydrogenation of p-chloronitrobenzene; panel b shows the conversion frequencies of various catalysts for the transfer hydrogenation of p-chloronitrobenzene. It can be seen from the figure that the catalyst prepared in example 1 has the best catalytic effect.
FIG. 17 is a graph showing the recycling performance of the catalyst prepared in example 1 in the p-chloronitrobenzene transfer hydrogenation reaction; it can be seen that the catalyst prepared in example 1 has good recycling performance in the p-chloronitrobenzene transfer hydrogenation reaction.
Table 2: structural features of catalyst # 1 to 3 and catalyst # 5
Catalyst S specific surface area (square per gram) V pore volume (cubic centimeter per gram) D aperture (nanometer)
Cu/OC 55.7 0.0052 7.95
Ni@OC 232.01 0.46 8.01
CuNi 0.05 @OC 99.38 0.13 5.68
CuNi 0.25 @OC 110.61 0.071 2.41
As can be seen from table 2, the specific surface area, pore volume, pore diameter of the catalyst prepared in example 1 are significantly different from those of the catalysts prepared in other examples. This is likely to have an unexpectedly large impact on the catalytic performance of the catalyst.
FIG. 18 is a surface potential analysis of the catalyst prepared in example 1; FIG. a) is CuNi 0.05 Atomic force microscopy image of OC, fig. b) is the corresponding three-dimensional image, fig. c) is the height distribution of the corresponding line in fig. a). FIG. d) shows the potential distribution of the corresponding line in FIG. e), which is CuNi 0.05 The surface potential of the @ OC catalyst, graph f) is the corresponding three-dimensional image.
Table 3:1# 3 catalyst and related thermodynamic parameters of 5# catalyst for p-chloronitrobenzene hydrogenation
In a 50mL round bottom flask containing 15mL deionized water, 20mg of catalyst # 1, 0.5mmol of each nitro compound, and 1.5mmol of hydrazine hydrate were added and reacted at 50℃for a period of time, and the reactants and products were qualitatively and quantitatively analyzed by GC and GC-MS, with the results shown in Table 4.
Table 4: no. 1 catalyst (CuNi 0.05 Transfer hydrogenation Performance for other nitro Compounds @ OC)
As can be seen from Table 4, the catalyst prepared in example 1 was excellent in transfer hydrogenation performance for different types of nitro compounds.
FIG. 19 is a graph showing the comparison of the performance of the catalyst prepared in examples 1-2 in the transfer hydrogenation of p-nitrophenol; FIG. a) shows the transfer hydrogenation of the catalyst according to example 2 on p-nitrophenol and FIG. b) shows the transfer hydrogenation of the catalyst according to example 1 on p-nitrophenol. As can be seen from FIG. 19, the performance of the catalyst prepared in example 1 in the transfer hydrogenation of p-nitrophenol was significantly better than that of the catalyst prepared in example 2.
In a 50mL autoclave containing 15mL deionized water, 20mg of the No. 1 catalyst and 0.75mmol of aldehyde compound are added, and 1.0MPaH is introduced after the air is exhausted 2 The reaction was carried out at 50℃for a period of time, and the products were subjected to qualitative and quantitative analysis by GC and GC-MS, and the results are shown in Table 5.
Table 5: no. 1 catalyst (CuNi 0.05 @ OC) for selective catalysis of furfural
As can be seen from table 5, the catalyst prepared in example 1 has excellent selective catalytic performance for furfural.
FIG. 20 is a graph showing the performance of the catalyst prepared in examples 1-2 in the hydrogenation of furfural. FIG. a) Cu/OC and CuNi 0.05 Comparative performance map of @ OC for low pressure hydrogenation of furfural; FIG. b is CuNi 0.05 The @ OC is used for a time evolution diagram of various products after the furfural hydrogenation reaction.
The foregoing has described the basic principles and main features of the present invention and the advantages of the present invention. It will be appreciated by persons skilled in the art that the scope of the invention is not limited by the embodiments described above. The present invention is subject to various changes and modifications without departing from the spirit and scope thereof, and such changes and modifications fall within the scope of the invention as hereinafter claimed.

Claims (10)

1. A catalyst for packaging rare alloy nano particles, which is characterized in that the catalyst takes oxygen doped porous carbon as a carrier, the rare alloy nano particles are packaged in the carrier, and the rare alloy nano particles comprise M metal and base metal Cu;
the M metal is at least one selected from Ni, co, zn, fe, V, ti;
the content of the M metal in the catalyst is 0.5-3.0wt%.
2. The catalyst of claim 1, wherein the rare alloy nanoparticles are comprised of Ni and Cu.
3. The catalyst according to claim 2, wherein the Cu content is 57.50-57.99wt% and the Ni content is 1.71-1.82wt%.
4. The catalyst according to claim 1, wherein the oxygen doping in the support means that oxygen is present in the grapheme-like carbon shell support in the form of hydroxyl oxygen or ether bond oxygen.
5. The catalyst of claim 1, wherein the pores in the support are predominantly mesoporous, microporous and macroporous.
6. The method for preparing the catalyst according to any one of claims 1 to 5, comprising the steps of:
1) Stirring and crystallizing a metal precursor, an oxygen-containing ligand, alkali and a solvent, and then separating to obtain a metal compound;
2) And (3) carrying out heat treatment on the metal compound obtained in the step (1) to obtain the catalyst.
7. The method according to claim 6, wherein in step 1), the metal precursor is M metal salt anda mixture of copper salts; and/or the copper salt is at least one of copper nitrate or hydrate thereof; and/or, in step 1), the oxygen-containing ligand is selected from at least one of benzoic acid, terephthalic acid, trimesic acid, 2-amino-1, 3, 5-benzene tricarboxylic acid; in step 1), the base is selected from CH 4 N 2 O、NaOH、KOH、NH 3 ·H 2 O、Na 2 CO 3 At least one of (a) and (b); in the step 2), the temperature of the heat treatment is 380-700 ℃.
8. The method according to claim 7, wherein the M metal salt is at least one selected from the group consisting of nickel nitrate, iron nitrate, cobalt nitrate, zinc nitrate, metavanadate, tetraethyl titanate, and hydrates thereof.
9. Use of the catalyst according to any one of claims 1 to 5 in a transfer hydrogenation reaction of nitro compounds with hydrazine hydrate or sodium borohydride as hydrogen source.
10. The catalyst of any one of claims 1-5 in H 2 Use in the directional hydrogenation of aldehydes which act as a source of hydrogen.
CN202311349195.6A 2023-10-16 2023-10-16 Catalyst for packaging rare alloy nano particles and preparation method and application thereof Pending CN117399012A (en)

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