The general formula is M+M x P y Stable and efficient synergistic catalyst for / PBNC and its preparation method and use

Abstract

This article relates to a general formula M+M x P y / PBNC consists of a multi-component carrier PBNC supporting a single-atom metal M and a cluster metal phosphide M. x P y A stable and efficient synergistic catalyst comprising, its preparation method and applications, wherein metal M, multi-component support PBNC and cluster metal phosphide M x P y As defined herein, the synergistic catalyst can be prepared by hydrothermal treatment of a support precursor, followed by impregnation with a soluble salt solution of metal M, oxygen-free thermal treatment under an inert atmosphere, and hydrogen reduction at a specific temperature. The synergistic catalyst provided herein can be used with high selectivity for catalytic hydrogenation under mild conditions.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalysts, more particularly to a stable and efficient synergistic catalyst composed of a single-atom metal supported by a multi-component carrier and a cluster metal phosphide, and a preparation method and use thereof. BACKGROUND

[0002] Catalysis and catalysts have been widely used in numerous industrial processes. Heterogeneous catalysts have the characteristics of stability, easy separation and recovery, and thus dominate large-scale industrial applications.

[0003] Traditional heterogeneous catalysts are prepared by simple impregnation or co-precipitation methods. However, the metal active centers on the surface of commonly used carriers such as activated carbon, TiO2, SiO2, etc. have problems of poor dispersion or uneven size, which is an important factor leading to poor repeatability in large-scale preparation of catalysts and significant reduction in the efficiency of catalysis, especially selective catalysis.

[0004] In addition, due to the lack of defects / sites for anchoring metals on the surface of traditional catalyst carriers, the interaction between the metal and the carrier is weak, and thus an inherent problem of metal nanoclusters used for catalytic applications is that they are thermodynamically unstable, which makes the surface energy of the metal particles increase sharply as the size of the metal particles decreases, and the metal species tends to strongly grow and sinter into larger grains. This metal sintering inevitably leads to a loss of active surface area or sites, resulting in deactivation of the catalyst.

[0005] In the past decade, considerable efforts have been made by those skilled in the art to inhibit the excessive sintering of metal nanoclusters. The most commonly used method is to confine the metal particles in the channels of mesoporous carriers (such as silica and carbon carriers); or use porous nanoshells (such as zeolites and metal oxides) to encapsulate metal nanoparticles. These are conceptually effective (avoiding partial sintering and growth of metal particles), but these methods have the problems of reducing the active surface area of the metal and increasing the mass transfer resistance, thus greatly reducing the overall performance of the catalyst.

[0006] Therefore, it is very important to develop a universal heterogeneous metal catalyst with high activity, high stability and high selectivity to promote the development of the catalytic industry. Accordingly, there is a need in the art to develop a highly active and stable heterogeneous catalyst with high selectivity and / or high yield in catalytic hydrogenation, especially selective catalytic hydrogenation, and the like. SUMMARY

[0007] The purpose of this invention is to solve some or all of the problems of the prior art mentioned above. By utilizing strong metal-support interaction (SMSI) and multiple heteroatom anchoring effect, it provides a supported catalyst with both activity and stability (especially thermodynamic stability) of metal single atoms and cluster metal phosphides with multiple active centers. It has the required catalytic performance such as high selectivity (up to 99% or more) and / or high yield in applications such as catalytic hydrogenation, especially selective catalytic hydrogenation.

[0008] Therefore, in one aspect, the present invention provides a general formula of M+M x P y / PBNC consists of a multi-component carrier PBNC supporting a single-atom metal M and a cluster metal phosphide M. x P y The synergistic catalyst consists of metal M selected from palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), nickel (Ni), copper (Cu), cobalt (Co), iron (Fe), zinc (Zn), aluminum (Al), tin (Sn), manganese (Mn), or molybdenum (Mo). The multi-component support PBNC is a multi-component support co-doped with phosphorus (P), boron (B), nitrogen (N), and carbon (C) atoms, and the cluster metal phosphide M... x P y It is a cluster complex formed by metal M and P in a multi-component support at an atomic molar ratio x:y, and the atomic molar ratio x:y is in the range of 0.1 to 10:1, preferably 0.25 to 7.5:1.

[0009] In a preferred embodiment, cluster metal phosphide M x P y The size is nanometer-sized, preferably ultrafine metal phosphides with a size of less than 2nm.

[0010] In a preferred embodiment, based on the total weight of the synergistic catalyst, it includes single-atom metal M and cluster metal phosphide M. x P y The loading of metal M, including metal M, is 0.5-10% by weight; preferably, when metal M is selected from Pd, Pt, Ru or Rh, the loading is 0.5-3% by weight, and when metal M is selected from Ni, Cu, Co, Fe, Zn, Al, Sn, Mn or Mo, the loading is 2-10% by weight.

[0011] In a preferred embodiment, in the multi-component carrier PBNC, the atomic molar ratio of P, B, N and C is 0.5∶1∶1∶1 to 1.8∶3.5∶2.5∶1 (typically based on the carbon (C) atoms therein).

[0012] In another aspect, the present application provides a method for preparing the above-mentioned synergistic catalyst, which comprises:

[0013] mixing and stirring the P-containing precursor, the B-containing precursor, the N-containing precursor and the C-containing precursor in water and subjecting them to hydrothermal treatment, and then drying to obtain a multi-component support PBNC precursor;

[0014] impregnating the multi-component support PBNC precursor with a solution of a soluble salt of metal M to obtain a supported precursor;

[0015] subjecting the obtained supported precursor to anaerobic heat treatment at a temperature of 600-800°C in an inert atmosphere to obtain a heat-treated precursor; and

[0016] subjecting the obtained heat-treated precursor to reduction treatment with H2 at a temperature of 400-600°C for 1-6h to obtain the desired synergistic catalyst.

[0017] In a preferred embodiment, the N-containing precursor and the C-containing precursor are provided by a precursor containing both N and C.

[0018] In a preferred embodiment, the B-containing precursor is mixed with the N-containing precursor and the C-containing precursor or the precursor containing both N and C, and then mixed with the P-containing precursor.

[0019] In a preferred embodiment, the hydrothermal treatment is carried out in a hydrothermal kettle at a temperature of 150-200°C for 4-15h.

[0020] In a preferred embodiment, the concentration of the solution of the soluble salt of metal M used is 0.5-10mmol / L; preferably, the impregnation time is 6-24h.

[0021] In a preferred embodiment, the supported precursor is dried at a temperature of 20-120°C for 1-12h before being subjected to anaerobic heat treatment; preferably, the anaerobic heat treatment is carried out for 1-5h.

[0022] In another aspect, the present application provides the use of the above-mentioned synergistic catalyst or the synergistic catalyst prepared according to the above-mentioned method for catalyzing hydrogenation, in particular catalyzing selective hydrogenation.

[0023] In a preferred embodiment, the synergistic catalyst is used for catalyzing hydrogenation, in particular catalyzing selective hydrogenation, at a H2 pressure of 0.1-5MPa and at a temperature of 0-180°C, preferably 20-120°C, more preferably 30-90°C, such as for catalyzing the hydrogenation of alkyne to olefin with a high selectivity of up to 99% or more, in particular for catalyzing the semi-hydrogenation of phenylacetylene to styrene.

[0024] In a preferred embodiment, the synergistic catalyst is used for the hydrogenation of levulinic acid to gamma-valerolactone and / or the hydrogenation of benzaldehyde to benzyl alcohol, preferably under milder catalytic hydrogenation conditions, such as lower H2 pressure and lower reaction temperature.

[0025] In a preferred embodiment, the reduction treatment with H2 is carried out with a mixture of an inert gas, such as N2, and H2.

[0026] The present application provides a synergistic catalyst with both high activity and stability by using a multi-component support PBNC co-doped with phosphorus (P), boron (B), nitrogen (N) and carbon (C), after loading metal components, through oxygen-free heat treatment followed by reduction treatment at a specific temperature, so that the surface of the multi-component support PBNC has abundant surface pore structure and metal anchoring sites (which ensures the formation of single-atom metal and its cluster metal phosphide on the surface of the support), and provides strong interaction between the metal component and the support, not only preventing the decline of catalytic activity caused by metal component agglomeration (i.e. binding the metal to prevent its excessive sintering and growth) and / or leaching (i.e. detachment from the surface of the support during use), but also introducing P atoms in the support into the metal clusters to form cluster metal phosphide M x P y , achieving the effect of stabilizing the metal species state and regulating the electronic state of the metal nanoparticles, thereby preparing a synergistic catalyst with both high activity and stability of single-atom metal and cluster metal phosphide multi-activity centers.

[0027] In addition, the interaction between the heteroatoms and the metal in the multi-component support can promote the uniform formation of multiple active sites coexisting with single-atom metal and cluster metal phosphide on the surface of the support, while the above-mentioned oxygen-free heat treatment and subsequent reduction treatment at a specific temperature can obtain nanoscale, especially sub-2 nm ultra-fine cluster metal phosphide, both single-atom metal and the corresponding ultra-small metal phosphide clusters have a synergistic effect, thereby can directionally regulate the efficiency of the catalyst, significantly promote the adsorption and activation of the substrate during the reaction process, while maintaining the ultra-small metal size, making it have both high activity and stability in catalytic hydrogenation (especially selective catalytic hydrogenation).

[0028] In particular, the synergistic catalyst of the present application can be used for catalytic hydrogenation (especially selective catalytic hydrogenation), for example, for the catalytic hydrogenation of alkynes to olefins with high selectivity of up to 99% or more, especially for the catalytic semi-hydrogenation of phenylacetylene to styrene, and can be used for the hydrogenation of levulinic acid to gamma-valerolactone and / or the hydrogenation of benzaldehyde to benzyl alcohol with high selectivity under milder conditions than conventional catalysts. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1A transmission electron microscope (TEM) image of the heat-treated precursor (i.e. after heat treatment) of the Ni precursor supported on the surface of the support PBNC precursor prepared according to one embodiment of the present application is shown;

[0030] Figure 2 A TEM image of the synergistic catalyst Ni + Ni2P / PBNC prepared according to one embodiment of the present application is shown, wherein the circles indicate the cluster Ni2P complexes supported on the support PBNC with a size below 2 nm;

[0031] Figure 3 An aberration-corrected electron microscope (AC-HAADF-STEM) image of the synergistic catalyst Ni + Ni2P / PBNC prepared according to one embodiment of the present application is shown, wherein the circles indicate the metal Ni single atoms supported on the support PBNC and the squares indicate the cluster Ni2P complexes supported on the support PBNC with a size below 2 nm;

[0032] Figure 4 An X-ray diffraction (XRD) pattern of the synergistic catalyst Ni + Ni2P / PBNC prepared according to one embodiment of the present application is shown;

[0033] Figure 5 Elemental mapping (EDS) images of the synergistic catalyst Ni + Ni2P / PBNC prepared according to one embodiment of the present application are shown, wherein image a represents another TEM image of the Ni + Ni2P / PBNC catalyst and images b-f represent the EDS images of the species elements Ni, P, B, N and C on the support surface shown in the TEM image of image a, respectively.

[0034] Figure 6 A TEM image of the synergistic catalyst Pd + Pd 15 P2 / PBNC prepared according to one embodiment of the present application is shown, wherein the circles indicate the cluster Pd 15 P2 complexes supported on the support PBNC with a size below 2 nm;

[0035] Figure 7 An aberration-corrected electron microscope (AC-HAADF-STEM) image of the synergistic catalyst Pd + Pd 15 P2 / PBNC prepared according to one embodiment of the present application is shown, wherein the circles indicate the metal Pd single atoms supported on the support PBNC and the squares indicate the cluster Pd 15 P2 complexes supported on the support PBNC with a size below 2 nm;

[0036] Figure 8 An X-ray diffraction (XRD) pattern of the synergistic catalyst Pd + Pd 15High resolution transmission electron microscopy (HRTEM) image of P2 / PBNC, where the boxes indicate clusters Pd with size below 2 nm supported on the support PBNC 15 Lattice spacing of P2 composite;

[0037] Figure 9 TEM image of the synergistic catalyst Co+CoP / PBNC prepared according to one embodiment of the application, where the circles indicate clusters CoP composite with size below 2 nm supported on the support PBNC;

[0038] Figure 10 TEM image of the synergistic catalyst Fe+FeP4 / PBNC prepared according to one embodiment of the application, where the circles indicate clusters FeP4 composite with size below 2 nm supported on the support PBNC;

[0039] Figure 11 TEM image of the synergistic catalyst Cu+Cu3P / PBNC prepared according to one embodiment of the application, where the circles indicate clusters Cu3P composite with size below 2 nm supported on the support PBNC;

[0040] Figure 12 TEM image of the synergistic catalyst Sn+Sn3P2 / PBNC prepared according to one embodiment of the application, where the circles indicate clusters Sn3P2 composite with size below 2 nm supported on the support PBNC;

[0041] Figure 13 TEM image of the synergistic catalyst Zn+Zn3P2 / PBNC prepared according to one embodiment of the application, where the circles indicate clusters Zn3P2 composite with size below 2 nm supported on the support PBNC;

[0042] Figure 14 TEM image of the synergistic catalyst Mn+Mn3P2 / PBNC prepared according to one embodiment of the application, where the circles indicate clusters Mn3P2 composite with size below 2 nm supported on the support PBNC;

[0043] Figure 15 TEM image of the synergistic catalyst Ru+RuP / PBNC prepared according to one embodiment of the application, where the circles indicate clusters RuP composite with size below 2 nm supported on the support PBNC; and

[0044] Figure 16 TEM image of the synergistic catalyst Pt+Pt5P2 / PBNC prepared according to one embodiment of the application, where the circles indicate clusters Pt5P2 composite with size below 2 nm supported on the support PBNC. DETAILED DESCRIPTION

[0045] The present inventors have recognized that, on one hand, reducing the particle size of the metal component on the surface of the heterogeneous catalyst carrier to the minimum, i.e. to single metal atom dispersion, can obtain a well-defined single-atom catalyst. The single-atom catalyst has 100% atom utilization efficiency, unique electronic and geometric properties, and exhibits excellent performance in numerous catalytic hydrogenation (especially selective catalytic hydrogenation) conversion processes. On the other hand, when the catalytic reaction requires more than one active site, the single-atom center cannot simultaneously adsorb and activate multiple substrates, resulting in low catalytic efficiency or even no reaction. In view of this, it is necessary to increase the abundance of active centers on a single-atom basis, and the preparation of a synergistic catalyst coexisting with single-atom metal and cluster metal compounds can provide sufficient active sites for the adsorption and activation of multiple substrates, thereby reducing the reaction barrier and thus improving the catalytic selectivity and activity. However, the present inventors have also recognized that the application of a synergistic catalyst coexisting with single-atom metal and cluster metal compounds mainly exists in two aspects of challenges: (1) lack of a simple and universal method for preparing a synergistic catalyst coexisting with single-atom metal and cluster metal compounds; (2) small-size metal cluster compounds are prone to sintering and growing under severe reaction conditions, resulting in a sharp decline in the stability and catalytic efficiency of the catalyst. Therefore, it is important to find new cluster sites with better performance and stability than traditional metal sites, and to develop a universal method for preparing a synergistic catalyst coexisting with single-atom metal and cluster metal compounds.

[0046] To this end, the present inventors have found through in-depth research that it is of great significance to increase the metal atom utilization and mass activity by reducing the metal to nanoscale. In particular, when the particle size is 2 nm or less, most of the metal atoms contained therein can be catalyzed, thereby improving the catalytic efficiency. More specifically, by using a multi-component carrier PBNC co-doped with phosphorus (P), boron (B), nitrogen (N) and carbon (C), after loading the metal component, through oxygen-free heat treatment followed by reduction treatment at a specific temperature, the surface of the multi-component carrier PBNC has a rich surface pore structure and provides strong interaction between the metal component and the carrier, which not only prevents the decline in catalytic activity caused by metal component agglomeration (i.e. binding the metal to prevent excessive sintering and growing) and / or leaching, but also introduces the activated P atoms in the carrier into the metal cluster to form cluster metal phosphide M x P y after reduction treatment, achieves the effect of stabilizing the metal species state and regulating the electronic state of the metal nanoparticles, and due to the anchoring effect of the multi-component heteroatoms, the corresponding metal phosphide cluster can be maintained in nanoscale, especially in the ultra-fine size range of 2 nm or less, thereby enabling the preparation of a catalyst coexisting with single-atom metal and novel metal phosphide cluster multi-active centers, which has both activity and stability.

[0047] Based on the above findings, the present application provides a multi-component heteroatom support-anchored single-atom metal and cluster metal phosphide synergistic catalyst, which is a synergistic catalyst composed of a multi-component support PBNC, a single-atom metal M and a cluster metal phosphide M x P y / PBNC, i.e. a synergistic catalyst composed of a multi-component support PBNC, a single-atom metal M and a cluster metal phosphide M x P y .

[0048] In the catalyst of the present application, the metal M can be selected from noble metals such as palladium (Pd), platinum (Pt), ruthenium (Ru) or rhodium (Rh), or non-noble metals such as nickel (Ni), copper (Cu), cobalt (Co), iron (Fe), zinc (Zn), aluminum (Al), tin (Sn), manganese (Mn) or molybdenum (Mo), depending on the specific application. If catalyst cost is a major consideration, the metal M in the catalyst of the present application can be selected only from non-noble metals; conversely, the metal M can be selected from noble metals or non-noble metals.

[0049] Preferably, the loading of the metal M (including the single-atom metal M and the cluster metal phosphide M x P y in the catalyst of the present application, based on the total weight of the catalyst, can be 0.5-10 wt%. More preferably, when the metal M is selected from Pd, Pt, Ru or Rh, the loading can be 0.5-3 wt%, and when the metal M is selected from Ni, Cu, Co, Fe, Zn, Al, Sn, Mn or Mo, the loading can be 2-10 wt%.

[0050] In the catalyst of the present application, the multi-component support PBNC is a multi-component support co-doped with phosphorus (P), boron (B), nitrogen (N) and carbon (C) atoms. Preferably, in the multi-component support PBNC, the atomic molar ratio of P, B, N and C can be 0.5:1:1:1-1.8:3.5:2.5:1 (typically based on C atoms). The present application has found that, at such an atomic molar ratio, the support obtained by the present application has a more abundant surface pore structure and heteroatom anchoring sites / defects, and provides stronger metal component-support interaction, thereby enabling better effects of stabilizing metal species state in the sub-nanometer range, regulating metal nanoparticle size, species and electronic state.

[0051] In the catalyst of the present application, the cluster metal phosphide M x P yto form a cluster complex of the metal M atom and the P atom in the support in an atomic molar ratio of x:y. Generally, the atomic molar ratio of the metal M atom to the P atom x:y can be in the range of 0.1-10:1, preferably 0.25-7.5:1. More particularly, x and y can be independently an integer of 1 to 15, in the case of satisfying the above molar ratio. Preferably, the cluster metal phosphide M x P y ultra-fine metal phosphide having a nano size, particularly 2 nm or less.

[0052] The above-described synergistic catalyst of the present application can be prepared by first mixing and stirring a P-containing precursor, a B-containing precursor, an N-containing precursor, and a C-containing precursor in water and subjecting to hydrothermal treatment, and then drying to obtain a multi-component support PBNC precursor; next, impregnating the multi-component support PBNC precursor with a solution of a soluble salt of the metal M to obtain a supported precursor; then, subjecting the obtained supported precursor to an oxygen-free heat treatment at a temperature of 600-800°C in an inert atmosphere to obtain a heat-treated precursor; and finally, subjecting the obtained heat-treated precursor to a reduction treatment with H2 at a temperature of 400-600°C for 1-6 h to obtain the desired synergistic catalyst.

[0053] Examples of the P-containing precursor that can be used in the method of the present application include, but are not limited to, phosphorus-containing compounds such as phosphoric acid, metaphosphoric acid, hypophosphorous acid, phosphorous acid, soluble phosphoric acid salts such as diammonium hydrogen phosphate, sodium phosphate, phosphoric acid esters, phytic acid, and the like, with phosphoric acid being preferably used.

[0054] Examples of the B-containing precursor that can be used in the method of the present application include, but are not limited to, boron-containing compounds such as boric acid, pyroboric acid, metaboric acid, soluble boric acid salts such as sodium borate, boric acid esters, and the like, with boric acid being preferably used.

[0055] The N-containing precursor that can be used in the method of the present application is any nitrogen-containing compound, and the C-containing precursor that can be used is any carbon-containing compound. Preferably, the N-containing precursor and the C-containing precursor used in the method of the present application are provided by a precursor compound containing both N and C. Examples of such precursor compounds can include, but are not limited to, melamine, 1,10-phenanthroline, and the like, with melamine being preferably used.

[0056] In the method of the present application, the B-containing precursor can be mixed with the N-containing precursor and the C-containing precursor (or the precursor containing both N and C) after mixing, and then mixed with the P-containing precursor. Preferably, the C-containing precursor, the N-containing precursor, the B-containing precursor, and the P-containing precursor are each mixed in an atomic molar ratio (C / N / B / P) of 1:1.5-3:2-4:1.2-1.8.

[0057] For example, when melamine is used as the precursor containing both N and C, boric acid is used as the precursor containing B and phosphoric acid is used as the precursor containing P, they can be mixed in a molar ratio of 1 : 2 ~ 4 : 1.2 ~ 1.8, more particularly in a molar ratio of 1 : 3 : 1.4. More particularly, in a flask with a water bath heating device (which temperature can be, for example, 75°C), melamine, boric acid are first added to an aqueous solution in the desired molar ratio and stirred to dissolve, and then phosphoric acid is added dropwise under stirring, and after white solid precipitates, it is kept for 10 ~ 60 min, for example, 30 min. After that, it is transferred to an autoclave and placed in an oven for hydrothermal treatment.

[0058] The hydrothermal treatment or hydrothermal reaction is well known in the art. In the method of the present application, for example, the hydrothermal treatment can be carried out in an autoclave in an oven at a temperature of 150 ~ 200°C, for example, 180°C for 4 ~ 15 h, for example, 12 or 13 h. Preferably, after the hydrothermal treatment is completed, the resulting product is subjected to a drying process, for example, in a drying oven at 105°C, thereby obtaining the support precursor.

[0059] In the method of the present application, the soluble salt of metal M that can be used can be, for example, a nitrate, acetate or chloride salt of the corresponding metal. Such a soluble salt can form a solution thereof by dissolving in a conventional solvent such as water, acetone, ethanol or a combination thereof, etc. Preferably, in the method of the present application, the concentration of the solution of the soluble salt of metal M used can be 0.5 ~ 10 mmol / L, such a concentration can be obtained, for example, by dissolving 0.1 mmol - 2 mmol of the soluble salt of metal in 200 mL of water, acetone or ethanol.

[0060] In the method of the present application, the impregnation operation with the solution of the soluble salt of metal M to impregnate the multi-component support PBNC precursor is known in the art, for example, it can be carried out by impregnating the aforementioned dried support precursor in a suitable container such as a beaker containing the solution of the soluble salt of metal M. Preferably, the time for impregnation can be 6 ~ 24 h, such as 12 - 24 h.

[0061] In the method of the present application, after the impregnation treatment is finished, the obtained supported precursor can be subjected to an oxygen-free heat treatment at a temperature of 600-800°C in an inert atmosphere to obtain a heat-treated precursor. Preferably, after the impregnation is finished, the obtained supported precursor is first dried in an oven, for example at a temperature of 20-120°C for 1-12h, and then subjected to the oxygen-free heat treatment. As used herein, the oxygen-free heat treatment means that the heat treatment is carried out in an inert atmosphere free of oxygen, such as N2atmosphere, for example heating to 700°C under oxygen-free conditions for 1-8h, such as 2h. The present inventors have found that by the oxygen-free heat treatment at such a temperature, the formation of oxides of the metal M and oxides of P, B, N and C in the support can be avoided as much as possible, thereby not only helping to form the desired porous support structure and abundant heteroatom anchoring sites, but also helping to obtain the desired monoatomic metal, multi-component atomic co-doped support and the complex of the metal M and P atoms by subsequent reduction treatment.

[0062] In the method of the present application, after the heat-treated precursor is obtained by the above-mentioned oxygen-free heat treatment, the obtained heat-treated precursor needs to be subjected to a reduction treatment with H2at a temperature of 400-600°C for 1-6h. The present inventors have found that by the above-mentioned oxygen-free heat treatment and the reduction treatment at the specific temperature, at least the following effects can be achieved: (1) the surface of the formed multi-component support PBNC has abundant surface porosity structure and heteroatom anchoring sites / defects, and thereby provides strong metal component-support interaction to anchor and adjust the species, size and electronic structure of the metal sites in the sub-nanometer range; (2) there are partial metal M monoatomic species on the surface of the support; (3) after the metal M monoatomic species are treated by the specific reduction conditions, multi-active center metal cluster sites are introduced around the metal M monoatomic species. At this time, the metal cluster sites, under the reduction atmosphere, are further subjected to reduction treatment, and the P element in the PBNC support is activated to combine with the metal cluster to evolve the metal cluster into more stable and better catalytic performance metal phosphide cluster sites; (4) such strong metal-support interaction and in-situ P activation strategy on the surface of the PBNC support can fully ensure that the ultrafine metal phosphide clusters exist on the surface of the support without excessive sintering to grow into large particles; (5) partial cluster species exist on the surface of the support and form metal phosphide cluster complexes with the P atoms in the support to coexist with the aforementioned monoatomic metal on the surface of the support; (6) the formed cluster metal complexes are nanoscale (especially below 2nm) small size metal cluster complexes; and (7) due to the formation of the above-mentioned support, the agglomeration (i.e. binding the metal to prevent it from sintering and growing) and / or leaching of the monoatomic metal component and the cluster complex can be prevented, and the metal species state can be stabilized and the metal nanocluster electronic state can be adjusted, thereby promoting the activity of selective catalytic hydrogenation.

[0063] The synergistic catalyst of the present application has various applications, including but not limited to catalyzing hydrogenation (especially selective catalytic hydrogenation) and the like. For example, the synergistic catalyst of the present application can be used for catalyzing hydrogenation (especially selective catalytic hydrogenation) under mild conditions, such as at a H2 pressure of 0.1-5 MPa, at a temperature of 0-180°C, preferably 20-120°C, more preferably 30-90°C. In particular, the synergistic catalyst of the present application can be used for catalyzing the hydrogenation of alkyne to olefin with a high selectivity of up to 99% or more, especially for catalyzing the semi-hydrogenation of phenylacetylene to styrene.

[0064] In addition, the synergistic catalyst of the present application can be used for conventional hydrogenation reactions, such as the hydrogenation of levulinic acid to γ-valerolactone and / or the hydrogenation of benzaldehyde to benzyl alcohol, with a high selectivity under conditions that are milder than conventional (e.g. lower H2 pressure, lower reaction temperature, etc.).

[0065] The present application will be described in detail below by way of non-limiting examples (including catalyst preparation examples and application examples). These examples are only used to illustrate the specific implementation and realization process of the present application, and are not used to limit the scope of the present application.

[0066] Unless otherwise specifically stated, the reaction apparatus, equipment, reaction reagents and operation process used in the following examples are all conventionally used in the art, and the reaction reagents or raw materials used therein can be directly used after purchase.

[0067] Preparation Example 1

[0068] Preparation of catalyst Ni+Ni2P / PBNC

[0069] A 1L flask equipped with a magnetic stirring device was placed in an oil bath (temperature set to 75°C), and 7g of melamine (National Pharmaceutical Group Chemical Reagent Co., Ltd.) and 10.416g of boric acid (National Pharmaceutical Group Chemical Reagent Co., Ltd.) were sequentially added to 500mL of deionized water. After stirring to dissolve, 7.4g of phosphoric acid (National Pharmaceutical Group Chemical Reagent Co., Ltd.) was added dropwise under stirring. After the addition was completed, the stirring was continued for 30min. Then, the obtained mixed solution was loaded into a 1000mL hydrothermal kettle (Anhui Kema Instrument Co., Ltd.), which was then moved into an oven (Anhui Kema Instrument Co., Ltd.) for hydrothermal reaction, wherein the temperature of the hydrothermal reaction was 180°C, and the time was 13 hours. After the hydrothermal kettle was completely cooled to room temperature, it was filtered by suction filtration and washed with water, and then dried in a drying oven at 105°C, thereby obtaining the PBNC carrier precursor.

[0070] Next, 8.0 g of the PBNC support precursor obtained above was immersed in 200 mL of an aqueous solution containing 280.4 mg of nickel nitrate hexahydrate in a 0.5 L flask placed in an oil bath pot with a temperature setting of 45°C, and stirred to reach adsorption equilibrium. Then, rotary evaporation was performed, followed by drying the residue in a drying oven at 105°C for 10 h, thereby obtaining a supported catalyst.

[0071] Next, the heat treatment precursor was subjected to a TEM analysis, and as a result, Figure 1 A TEM image of the heat treatment precursor prepared is shown. From Figure 1 It can be seen that no particles or clusters of metals appear, indicating that the support PBNC prepared has a strong metal anchoring ability, which can prevent the metal from excessive agglomeration and overgrowth, thereby maintaining a high degree of dispersibility.

[0072] Finally, in a sealed tube furnace, a mixed gas of nitrogen and hydrogen (N2 / H2, the volume ratio of the two is 9:1; obtained from Nanjing Special Gas Co., Ltd.) was introduced, and the temperature was programmed to 400°C at a rate of 1°C / min for reduction for 4 h, thereby obtaining a catalyst Ni+Ni2P / PBNC, and the nickel loading of the catalyst (based on the total weight of the catalyst, in terms of Ni atoms) was determined to be 2% by inductively coupled plasma emission spectrometry (ICP) test.

[0073] The obtained catalyst Ni+Ni2P / PBNC was subjected to TEM analysis and XRD analysis, and as a result, Figure 2 A TEM image of the obtained catalyst Ni+Ni2P / PBNC is shown, Figure 3 An AC-HAADF-STEM image of the obtained catalyst Ni+Ni2P / PBNC is shown, Figure 4 An XRD image of the obtained catalyst Ni+Ni2P / PBNC is shown, and Figure 5 An EDS image of the obtained catalyst Ni+Ni2P / PBNC is shown.

[0074] From Figure 2 It can be seen that in the catalyst Ni+Ni2P / PBNC obtained in the present application, the nickel species is uniformly dispersed on the support, which indicates that the nickel species has good dispersibility. Based on the TEM test results, the particle size statistics was performed using Nano Measure software, and the average particle size of the Ni species was 1.25 nm, which indicates that the PBNC support with multiple component heteroatoms can uniformly disperse the Ni species. Figure 3The AC-HAADF-STEM image of the PBNC support shows that there are uniformly dispersed metal Ni monomers and clusters on the surface of the PBNC support, and the metal Ni monomers are uniformly distributed around the clusters. Figure 4 The XRD image of the PBNC support shows that there are small cluster Ni2P compound diffraction peaks, which indicates that there is a Ni2P species on the PBNC support. Figure 5 The element distribution of the obtained catalyst Ni+Ni2P / PBNC can be clearly seen, which shows the uniform distribution of P, B, N, C elements and the real existence of Ni element. Combined with the analysis results of these XRD, TEM, AC-HAADF-STEM, the present application can use the PBNC support with multi-component heteroatoms to anchor the metal precursor, and a synergistic catalyst of metal Ni monomers and 2nm or less cluster metal phosphide Ni2P is prepared.

[0075] Therefore, it is proved that, by the preparation method of the present application, after the metal Ni precursor is impregnated with the PBNC support, the multi-component heteroatom support PBNC can fully anchor the Ni species to make it uniformly dispersed; then, the further reduction treatment of hydrogen H2 significantly promotes the conversion of metal Ni to Ni2P species, so that the uniformly dispersed Ni monomers and 2nm or less size ultrafine Ni2P clusters are formed on the surface of the PBNC support, which has a strong metal-support interaction, thereby preventing the excessive agglomeration of metal Ni and leaching in use. Without being bound by theory, it is believed that this leads to the obtained catalyst to exhibit better catalytic activity and stability.

[0076] Preparation Example 2

[0077] Catalyst Pd+Pd 15 Preparation of P2 / PBNC (Pd loading amount is 0.5wt%)

[0078] First, the PBNC precursor is prepared as described in Preparation Example 1.

[0079] Next, 8.0g of the obtained PBNC support precursor is impregnated into 200mL of an acetone solution containing 30.8mg of palladium acetate (National Pharmaceutical Group Chemical Reagent Co., Ltd.) in a flask placed and fixed in an oil bath pot (temperature setting is 45℃), and stirred for 24h to achieve adsorption equilibrium. Then, rotary evaporation is performed, and then the residue is dried in a drying box at 105℃ for 10h, thereby obtaining a supported carrier.

[0080] Next, the oxygen-free heat treatment is carried out in a sealed tube furnace under a nitrogen atmosphere by heating to 700℃ at a heating rate of 3℃ / min, and then heating for 2h, thereby obtaining a heat-treated precursor.

[0081] Finally, the obtained catalyst Pd+Pd 15 P2 / PBNC was subjected to TEM analysis, as a result,

[0082] The obtained catalyst Pd+Pd 15 P2 / PBNC was subjected to TEM analysis, as a result, Figure 6 The TEM image of the obtained catalyst Pd+Pd ls P2 / PBNC is shown, Figure 7 The AC-HAADF-STEM image of the obtained catalyst Pd+Pd 15 P2 / PBNC is shown, Figure 8 The HRTEM image of the obtained catalyst Pd+Pd 15 P2 / PBNC is shown, in which the Pd+Pd 15 P2 species in P2 / PBNC is shown. ls P2 is shown.

[0083] From the above, Figures 6 to 8 It can be seen that in the catalyst Pd+Pd 15 P2 / PBNC obtained by the present application, the Pd species is uniformly dispersed on the support, and the average particle size of the Pd species is 1.2 nm, which indicates that the PBNC support with multiple-component heteroatoms can uniformly disperse the Pd species. Figure 7 The AC-HAADF-STEM image of P2 / PBNC shows that there are Pd monomers and clusters uniformly dispersed on the surface of the PBNC support, and the monomers are uniformly distributed around the clusters. Figure 8 The HRTEM image of P2 / PBNC shows that there are clear Pd 15 P2 lattice spacings (0.230 nm), which indicates that there are Pd l5 P2 species on the PBNC support. In combination with the results of TEM, AC-HAADF-STEM and HRTEM analysis, it is shown that the present application uses the PBNC support with multiple-component heteroatoms to anchor the metal precursor, which can be used to universally prepare the catalyst with Pd monomers and cluster metal phosphide Pd ls P2 synergistically.

[0084] It is thus confirmed that by the preparation method of the present application, after the metal Pd precursor is impregnated with the support PBNC, and then subjected to oxygen-free heat treatment, the multiple-component heteroatom support PBNC fully anchors the Pd species to make it uniformly dispersed; and then subjected to further reduction treatment with hydrogen, which significantly promotes the metal Pd to Pd lsP2 species transformation, thus forming uniformly dispersed Pd monatomic and small size Pd ls P2 clusters, with strong metal-support interaction, thus preventing metal Pd agglomeration and leaching, which leads to the resulting synergistic catalysts exhibiting better catalytic activity and stability.

[0085] Preparation Example 3-10

[0086] In the same procedure as described above in Preparation Example 1 or Preparation Example 2, by loading appropriate amount of cobalt (Co o ), iron (Fe), copper (Cu), tin (Sn), zinc (Zn), manganese (Mn), ruthenium (Ru), platinum (Pt) onto the PBNC support, respectively, the following synergistic catalysts Co+CoP / PBNC (Co loading amount is 4.5%), Fe+FeP4 / PBNC (Fe loading amount is 10%), Cu+Cu3P / PBNC (Cu loading amount is 10%), Sn+Sn3P2 / PBNC (Sn loading amount is 4.5%), Zn+Zn3P2 / PBNC (Zn loading amount is 4.5%), Mn+Mn3P2 / PBNC (Mn loading amount is 4.5%), Ru+RuP / PBNC (Ru loading amount is 3%), Pt+Pt5P2 / PBNC (Pt loading amount is 1.5%) were obtained. They were characterized by high resolution transmission electron microscopy (HRTEM), respectively, and the results are shown in Figures 9 to 16 As can be seen from Figures 9 to 16 , there are uniformly dispersed corresponding monatomic metals and corresponding cluster metal complexes (ultra-fine cluster metal complexes with a size of 2 nm or less) on the surface of the PBNC support of each of the Co+CoP / PBNC, Fe+FeP4 / PBNC, Cu+Cu3P / PBNC, Sn+Sn3P2 / PBNC, Zn+Zn3P2 / PBNC, Mn+Mn3P2 / PBNC, Ru+RuP / PBNC, Pt+Pt5P2 / PBNC catalysts.

[0087] Preparation Comparative Example 1-20

[0088] In the same procedure as Preparation Example 1, metal Ni and Pd were loaded onto the active carbon (C), nitrogen-carbon doped support (NC), boron-nitrogen-carbon doped support (BNC), phosphorus-nitrogen-carbon doped support (PNC), MgO, CeO2, ZrO2, TiO2, Al2O3, SiO2 supports, respectively, with a loading amount of 2% and 0.5%, respectively, to obtain supported catalysts on different supports. Among them, the preparation process of the above NC, BNC, PNC supports is the same as that of Preparation Example 1, only the corresponding precursors required are used for preparation; while the other conventional supports of activated carbon and oxide supports can be obtained from Sinopharm Chemical Reagent Co., Ltd.

[0089] Application Example 1

[0090] Application for catalyzing semi-hydrogenation of phenylacetylene to prepare styrene

[0091]

[0092] The catalytic reaction process is as follows: 510.5 mg of reaction substrate phenylacetylene (Shanghai Aladdin Biochem Technology Co., Ltd.) and 50 mg of the catalyst prepared in Preparation Example 1 are added into a 25 mL reaction kettle under magnetic stirring, and ethanol is added to adjust the reaction substrate concentration to 5% by weight. The reaction kettle is first flushed with 1 MPa of H2 and then discharged (repeated 5 times) to remove the internal air, and finally filled with H2 to 1 MPa. The reaction is carried out under stirring at 30°C. After 8 hours of reaction, the reaction liquid is cooled, degassed, and filtered to separate the catalyst from the reaction liquid. After diluting the reaction liquid with ethanol, 50 mg of bicyclohexane (Shanghai Aladdin Biochem Technology Co., Ltd.) is added as an internal standard, and gas chromatography analysis is performed.

[0093] The gas chromatography conditions are as follows: GC1690 gas chromatograph with FID detector, capillary chromatographic column (Innowax, 30 m x 0.250 mm x 0.25 μm), and programmed temperature rise with initial column temperature of 50°C, temperature rise rate of 10°C / min to 250°C for 10 min. The carrier gas is 99.99% high-purity N2 with a flow rate of 1 mL / min. The reactant conversion rate and product selectivity are calculated according to the gas chromatography detection results, and the results are shown in Table 1.

[0094] Application Examples 2-7

[0095] Application for catalyzing semi-hydrogenation of phenylacetylene to prepare styrene

[0096] Using the reaction conditions listed in Table 1, the catalysts Pd+Pd15P2 / PBNC, Pt+Pt5P2 / PBNC, Ru+RuP / PBNC, Co+CoP / PBNC, Fe+FeP4 / PBNC and Cu+Cu3P / PBNC prepared above are used to catalyze semi-hydrogenation of phenylacetylene to prepare styrene according to the reaction process described in Application Example 1, wherein the reaction substrate concentration is 5% by weight and the hydrogen pressure is maintained at 1 MPa. After the reaction, the reactant conversion rate and product selectivity are calculated according to the gas chromatography detection results, and the results are shown in Table 1.

[0097] Table 1

[0098]

[0099]

[0100] Application Comparative Examples 1-20

[0101] Use for catalyzing semi-hydrogenation of phenylacetylene to prepare styrene

[0102] Using the reaction conditions listed in Table 2, the catalysts prepared in Preparation Examples 1-20 above were used respectively to catalyze semi-hydrogenation of phenylacetylene to prepare styrene according to the reaction process described in Application Example 1, wherein the reaction substrate concentration was 5 wt% and the hydrogen pressure was maintained at 1 MPa. After the reaction was completed, the conversion of the reactant and the selectivity of the product were calculated according to the detection results by gas chromatography, and the results are shown in Table 2.

[0103] Table 2

[0104]

[0105]

[0106] It is to be noted that in the reaction of selective hydrogenation of phenylacetylene to prepare styrene, the target product styrene is easy to be over-hydrogenated to form ethylbenzene. However, as can be seen from the results of Table 1 and Table 2 above, under the same metal and the same loading, and under the same reaction temperature and time, the conversion and the selectivity to styrene in the reaction of catalyzing hydrogenation of phenylacetylene to obtain the target product styrene are all lower for the carrier without heteroatoms (i.e. activated carbon), the carrier co-doped with one or two heteroatoms (i.e. NC, BNC and PNC), and the conventional oxide supported catalyst (Application Comparative Examples 1-20) than for the catalysts of the present application (Application Examples 1-7), which confirms that under the same conditions, the catalysts provided by the present application are much superior to the conventional catalysts.

[0107] Application Examples 8-14

[0108] Use for catalyzing semi-hydrogenation of phenylacetylene to prepare styrene

[0109] Using the reaction conditions listed in Table 3, the reaction process described in Application Example 1 was used to catalyze semi-hydrogenation of phenylacetylene to prepare styrene, wherein the reaction substrate concentration was 5 wt% and the hydrogen pressure was maintained at 1 MPa. After the reaction was completed, the conversion of the reactant and the selectivity of the product were calculated according to the detection results by gas chromatography, and the results are shown in Table 3.

[0110] Table 3

[0111]

[0112] Application Examples 15-21

[0113] Use for catalyzing semi-hydrogenation of phenylacetylene to prepare styrene

[0114] The catalytic semi-hydrogenation of phenylacetylene to styrene was carried out according to the reaction procedure described in Application Example 1 under the reaction conditions listed in Table 4, with a reaction substrate concentration of 5 wt% and a hydrogen pressure of 1 MPa. The conversion of the reactant and the selectivity of the product were calculated from the results of the gas chromatography detection after the reaction was completed, and the results are shown in Table 4.

[0115] Table 4

[0116]

[0117] Application Examples 22-28

[0118] Catalytic hydrogenation of levulinic acid to γ-valerolactone

[0119]

[0120] The catalytic reaction procedure was as follows: 348.4 mg of the reaction substrate levulinic acid (Shanghai Aldrin Biochemical Technology Co., Ltd.) and 50 mg of the catalyst in Table 5 were added to a 25 mL reaction kettle under magnetic stirring, and ethanol was added to adjust the reaction substrate concentration to 3 wt%. The internal air was removed by first flushing 1 MPa H2 into the reaction kettle and then discharging it (repeated 5 times), and finally H2 was filled to 1 MPa. The reaction was carried out under stirring at 90°C. After 5 h of reaction, the catalyst was separated from the reaction solution by cooling, releasing the gas and filtering. After diluting the reaction solution with ethanol, 50 mg of n-hexanol (Shanghai Aldrin Biochemical Technology Co., Ltd.) was added as an internal standard, and the solution was analyzed by gas chromatography.

[0121] The gas chromatography conditions were as follows: GC1690 gas chromatograph with FID detector, capillary chromatographic column (Innowax, 30 m x 0.250 mm x 0.25 μm), with programmed temperature rise, initial column temperature of 50°C, and temperature rise rate of 10°C / min to 250°C for 10 min. The carrier gas was 99.99% high-purity N2, and the flow rate was 1 mL / min. The conversion of the reactant and the selectivity of the product were calculated from the results of the gas chromatography detection, and the results are shown in Table 5.

[0122] Table 5

[0123]

[0124] Application Examples 29-42

[0125] Catalytic hydrogenation of levulinic acid to γ-valerolactone

[0126] The catalytic hydrogenation reaction was carried out according to the reaction process described in application examples 22-28 using the reaction conditions (catalyst used, reaction temperature, hydrogen pressure and time) listed in Table 6, with a reaction substrate concentration of 3 wt%. After the reaction, the conversion of the reactant and the selectivity of the product were calculated according to the gas chromatography detection results, and the results are shown in Table 6.

[0127] Table 6

[0128]

[0129]

[0130] Application examples 43-49

[0131] Catalytic hydrogenation of benzaldehyde to prepare benzyl alcohol

[0132]

[0133] The catalytic reaction process was as follows: 318.4 mg of reaction substrate benzaldehyde (Shanghai Aladdin Biochem Technology Co., Ltd.) and 50 mg of catalyst in Table 7 were added to a 25 mL reaction kettle under magnetic stirring, and ethanol was added to adjust the reaction substrate concentration to 3 wt%. The internal air was discharged by first flushing 1 MPa H2 into the reaction kettle and then discharging (repeated 5 times), and finally H2 was filled to 1 MPa. The reaction was carried out at 90°C under stirring conditions. After 5h of reaction, the catalyst was separated from the reaction solution by cooling, degassing and filtering. After diluting the reaction solution with ethanol, 50 mg of n-hexanol (Shanghai Aladdin Biochem Technology Co., Ltd.) was added as an internal standard, and the reaction solution was analyzed by gas chromatography.

[0134] The gas chromatography conditions were as follows: GC1690 gas chromatography FID detector, capillary chromatographic column (Innowax, 30 m x 0.250 mm x 0.25 μm), with programmed temperature rise, initial column temperature 50°C, with a temperature rise rate of 10°C / min to 250°C for 10 min. The carrier gas was 99.99% high-purity N2 with a flow rate of 1 mL / min. The conversion of the reactant and the selectivity of the product were calculated according to the gas chromatography detection results, and the results are shown in Table 7.

[0135] Table 7

[0136]

[0137]

[0138] Application examples 50-63

[0139] Catalytic hydrogenation of benzaldehyde to prepare benzyl alcohol

[0140] The catalytic hydrogenation reaction was carried out according to the reaction process described in application examples 31-38 using the reaction conditions (catalyst used, reaction temperature, hydrogen pressure and time) listed in Table 8, wherein the reaction substrate concentration was 3 wt%. After the reaction, the conversion of the reactant and the selectivity of the product were calculated according to the gas chromatography detection results, and the results are shown in Table 8.

[0141] Table 8

[0142]

[0143] The above results show that the PBNC carrier with multiple component heteroatoms and metals such as palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium (Rh), nickel (Ni), copper (Cu), cobalt (Co), iron (Fe), zinc (Zn), aluminum (Al), tin (Sn), manganese (Mn), molybdenum (Mo) and the like are obtained by a specific preparation process, which has a strong single atom-cluster synergistic effect. The process is simple and easy to operate, the product and catalyst are easy to separate, the catalyst is easy to obtain and has a strong single atom-cluster synergistic effect, and has a very wide application prospect in the field of catalytic hydrogenation (especially catalytic selective hydrogenation).

[0144] In addition, the above results also show that the synergistic catalyst provided by the present application can catalyze the hydrogenation of the target product with high selectivity / yield (up to 99%, even up to 100%) under relatively mild conditions. Using the catalyst of the present application, the process for preparing styrene, γ-valerolactone, benzyl alcohol and other bulk platform molecules is simple, the reaction equipment is simple, the operation is simple, the product and catalyst are easy to separate, the catalyst is cheap and easy to obtain, the catalyst has good hydrothermal stability and recycling performance, and is suitable for industrial production, and has a very wide application prospect.

[0145] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A synergistic catalyst of the formula M + M x P y / PBNC, wherein the metal M is selected from Pd, Pt, Ru, Rh, Ni, Cu, Co, Fe, Zn, Al, Sn, Mn or Mo, the multi-component support PBNC is a multi-component support co-doped with P, B, N and C atoms, and the cluster metal phosphide M x P y is a cluster complex of the metal M and P in the multi-component support in an atomic molar ratio x : y, and the atomic molar ratio x : y is in the range of 0.1 to 10 : 1, the cluster metal phosphide M x P y has a size in the nanometer range. x P y ​ 2. The synergistic catalyst according to claim 1, characterized in that, The cluster metal phosphide M x P y Ultrafine metal phosphide having a size of 2 nm or less.

3. The synergistic catalyst of claim 1, wherein The metal M, including the monatomic metal M and the cluster metal phosphide M x P y The loading of the metal M, including the metal M in the monatomic metal M and the cluster metal phosphide M, is 0.5-10 wt.%.

4. The synergistic catalyst according to claim 3, characterized in that, The loading amount is 0.5-3 wt% when the metal M is selected from Pd, Pt, Ru or Rh, and the loading amount is 2-10 wt% when the metal M is selected from Ni, Cu, Co, Fe, Zn, Al, Sn, Mn or Mo.

5. The synergistic catalyst of claim 1, wherein In the multi-component support PBNC, the atomic molar ratio of P, B, N and C is 0.5:1:1:1~1.8:3.5:2.5:

1.

6. A method for preparing the synergistic catalyst according to any one of claims 1 to 5, the method comprising: stirring and mixing P-containing precursor, B-containing precursor, N-containing precursor and C-containing precursor in water and subjecting to hydrothermal treatment, and then drying to obtain a multi-component support PBNC precursor; impregnating the multi-component support PBNC precursor with a solution of soluble salt of the metal M to obtain a supported precursor; subjecting the obtained supported precursor to anaerobic heat treatment at a temperature of 600~800℃ in an inert atmosphere to obtain a heat-treated precursor; and subjecting the obtained heat-treated precursor to reduction treatment with H2 at a temperature of 400-600℃ for 1-6h to obtain the desired synergistic catalyst.

7. The method of claim 6, wherein, The N-containing precursor and the C-containing precursor are provided by N- and C-containing precursors.

8. The method of claim 7, wherein, The B-containing precursor is mixed with the N-containing precursor and the C-containing precursor or the N- and C-containing precursors, and then mixed with the P-containing precursor.

9. The method of claim 7, wherein, The hydrothermal treatment is carried out in an autoclave at a temperature of 150~200℃ for 4~15h.

10. The method of claim 6, wherein, The concentration of the solution of soluble salt of the metal M used is 0.5~10 mmol / L.

11. The method of claim 10, wherein, The impregnation time is 6~24h.

12. The method of claim 6, wherein, The supported precursor is dried at a temperature of 20-120℃ for 1-12h before being subjected to anaerobic heat treatment.

13. The method of claim 12, wherein, The anaerobic heat treatment is carried out for 1~5h.

14. Use of the synergistic catalyst according to any one of claims 1 to 5 or prepared according to the method of any one of claims 6 to 13 for catalyzing hydrogenation.

15. Use according to claim 14, characterized in that, The use is for catalyzing selective hydrogenation.

16. Use according to claim 14 or 15, characterized in that, The synergistic catalyst is used for catalyzing hydrogenation at a temperature of 0-180℃ under a H2 pressure of 0.1-5MPa.

17. Use according to claim 16, characterized in that, The synergistic catalyst is used for catalyzing hydrogenation at a temperature of 20-120℃.

18. Use according to claim 17, characterized in that, The synergistic catalyst is used for catalyzing hydrogenation at a temperature of 30-90℃.

19. Use according to claim 16, characterized in that, The synergistic catalyst is used for catalyzing the hydrogenation of alkyne to olefin with high selectivity of up to 99%.

20. The use according to claim 16, characterized in that, The synergistic catalyst is used for catalyzing the semi-hydrogenation of phenylacetylene to styrene.

21. The use according to claim 16, characterized in that, The synergistic catalyst is used for catalyzing the hydrogenation of levulinic acid to γ-valerolactone and / or the hydrogenation of benzaldehyde to benzyl alcohol. The synergistic catalyst is used for catalyzing the hydrogenation of levulinic acid to γ-valerolactone and / or the hydrogenation of benzaldehyde to benzyl alcohol.

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