Metal/alpha-MoC1-X load-type single-atomic dispersion catalyst, synthesis method and applications

Abstract

A metal/α-MoC.sub.1-x load-type single-atomic dispersion catalyst, a synthesis method therefor, and applications thereof. The catalyst uses α-MoC.sub.1-x as carrier, and has metal that has the mass fraction ranging from 1-100% and that is dispersed on carrier α-MoC.sub.1-x in the single atom form. The catalyst provided in the present application can be adapted to a wide alcohol/water proportion in hydrogen production based on aqueous-phase reforming of alcohols, outstanding hydrogen production performance can be obtained at a variety of proportions, and catalysis performance of the catalyst is much higher than that of metal loaded with an oxide carrier. Especially when the metal is Pt, catalysis performance of the catalyst provided in the present application in the hydrogen production based on aqueous-phase reforming of alcohols is much higher than that of a Pt/α-MoC.sub.1-x load-type catalyst on the α-MoC.sub.1-x carrier on which Pt is disposed on a layer form in the prior art. The hydrogen production performance of the catalyst provided in the present application can be higher than 20,000 h.sup.−1 at the temperature of 190° C.

Claims

1. A catalyst comprising: a metal and α-MoC.sub.1-x, wherein the α-MoC.sub.1-x is a support and the metal is an active component dispersed on the α-MoC.sub.1-x support, wherein 10-100% of the metal dispersed on the α-MoC.sub.1-x support is in a single-atomic form, wherein in the α-MoC.sub.1-x support, x is 0-0.9, and wherein the metal is at least one selected from the group consisting of platinum, ruthenium, palladium, nickel, copper, and cobalt.

2. The catalyst of claim 1, wherein 90-100% of the metal dispersed on the α-MoC.sub.1-x support is in a single-atomic form.

3. The catalyst of claim 1, wherein the metal dispersed on the α-MoC.sub.1-x support is 0.01-50% by mass, based on a total mass of the α-MoC.sub.1-x support with the metal dispersed thereon.

4. The catalyst of claim 1, wherein the metal dispersed on the α-MoC.sub.1-x support is 0.01-10% by mass, based on a total mass of the α-MoC.sub.1-x support with the metal dispersed thereon.

5. The catalyst of claim 1, wherein the α-MoC.sub.1-x support has a size of between 1-30 nm.

6. The catalyst of claim 1, wherein the α-MoC.sub.1-x support has a specific surface area of between 5-250 m.sup.2/g.

7. A method for preparing the catalyst of claim 1, comprising: 1) synthesizing the α-MoC.sub.1-x support; 2) dissolving a metal precursor salt to obtain a metal precursor salt solution, wherein the metal precursor salt is a precursor salt of the metal; 3) mixing the metal precursor salt solution in step 2) with the α-MoC.sub.1-x support in step 1) to form a mixture; 4) drying the mixture to obtain a solid, wherein the metal of the metal precursor salt has a mass of between 0.01%-55% of a mass of the α-MoC.sub.1-x support with the metal precursor salt mixed thereon; 5) lyophilizing the obtained solid in step 3) to obtain a catalyst precursor; and 6) carburizing the catalyst precursor in a carburization gas atmosphere containing both a carbon source and a hydrogen source to obtain the catalyst.

8. The method of claim 7, wherein the metal precursor salt is a water-soluble salt.

9. The method of claim 8, wherein the metal precursor salt is at least one selected from the group consisting of dipotassium tetrachloroplatinate, disodium tetrachloroplatinate, platinum bis(acetylacetonate), chloroplatinic acid, palladium chloride, palladium acetate, nickel chloride, copper chloride, cobalt chloride, nickel nitrate, copper nitrate, cobalt nitrate, nickel acetylacetonate, copper acetylacetonate, and cobalt acetylacetonate.

10. The method of claim 7, wherein the metal precursor salt comprises the metal having a mass of between 0.01%-12% of a total mass of the α-MoC.sub.1-x support with the metal precursor salt thereon.

11. The method of claim 7, wherein: the carbon source is at least one selected from the group consisting of alkane, olefin and alcohol; the hydrogen source is hydrogen gas; the volume ratio of the carbon source to the hydrogen source is of between 0.1:9 to 9:1; the heating rate of temperature programming for carburization is 1-50° C./min; and the carburization comprises a highest temperature step of between 490-900° C.

12. The method of claim 11, wherein the carburization comprises a temperature step performed at between 200-300° C. for of between 0.1-50 hours and the highest temperature step is then performed of between 490-900° C. for of between 0.1-100 hours.

13. Use of the catalyst of claim 1 for the hydrogen production reaction of an alcohol aqueous phase reforming, comprising: contacting the catalyst with an aqueous solution of an alcohol in a closed system at a reaction temperature to produce hydrogen.

14. The use of claim 13, wherein the alcohol is selected from the group consisting of methanol, ethanol, glycerin and ethylene glycol.

15. The use of claim 13, wherein the reaction temperature of the hydrogen production reaction of the alcohol aqueous phase reforming is of between 50-280° C.

16. The use of claim 13, wherein the aqueous solution of the alcohol comprises the alcohol and water in a ratio of between 0.1:9 to 10:1.

Description

DESCRIPTION OF THE DRAWINGS

(1) In order to illustrate the examples of the present application and the technical solutions of the prior art more clearly, the drawings that need to use in the examples and the prior art will be briefly introduced. Obviously, the drawings described following are only some examples of the present application, and those skilled in the art can obtain other drawings according to these drawings without any creative work.

(2) FIG. 1 is an XRD pattern of the support α-MoC.sub.1-x prepared in Example 1 and the catalysts prepared in Examples 2, 5, 6, 7, 8, and 9, wherein (a) in FIG. 1 is an XRD pattern of support α-MoC.sub.1-x prepared in Example 1; (b) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 2; (c) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 5; (d) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 6; (e) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 7; (f) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 8; and (g) in FIG. 1 is an XRD pattern of the catalyst prepared in Example 9;

(3) FIG. 2A is a scanning transmission electron micrograph of the catalyst prepared in Example 2 before the catalytic reaction;

(4) FIG. 2B is a scanning transmission electron micrograph of the catalyst prepared in Example 2 after the catalytic reaction;

(5) FIG. 3 is an X-ray absorption fine structure (XAFS) spectrum characterization result of the catalyst prepared in Example 2, wherein (a) in FIG. 3 is an EXAFS fitting graph of the Pt L3 absorption edge in the catalyst before the catalytic reaction; (b) in FIG. 3 is an EXAFS fitting graph of the Pt L3 absorption edge in the catalyst after the catalytic reaction; (c) in FIG. 3 is an XANES fitting graph of the Pt L3 absorption edge in the catalyst before and after the reaction; and (d) in FIG. 3 is an XANES graph of the Mo K absorption edge in the catalyst before and after the reaction;

(6) FIG. 4 is a scanning transmission electron micrograph of the catalyst prepared in Example 3;

(7) FIG. 5 is a scanning transmission electron micrograph of the catalyst prepared in Example 4;

(8) FIG. 6 is a scanning transmission electron micrograph of the catalyst prepared in Example 10, wherein a and b are scanning transmission electron micrographs at different scales respectively;

(9) FIG. 7 is a catalytic effect graph of the catalyst prepared in Example 2 in a plurality of repeated catalytic reactions;

(10) FIG. 8 is a graph showing the catalytic activity of the catalysts prepared in Example 7 and Comparative Example 3 at different temperatures;

(11) FIG. 9 is a graph showing the optimization of the molar ratio of methanol to water for the catalyst prepared in Example 2;

(12) FIG. 10 is a graph showing the optimization of the molar ratio of methanol to water for the catalyst prepared in Example 7.

DETAILED DESCRIPTION OF THE INVENTION

(13) In order to illustrate the objects, the technical solutions, and the advantages of the present application more clearly, the present application will be further described in detail below with reference to the drawings and examples. It is apparent that the described examples are only a part of the examples of the present application, not all of examples. All other examples obtained by the ordinary skilled in the art without creative work based on the examples of the present application are within the scope of the present application.

EXAMPLE 1

Preparation of Support α-MoC.SUB.1-x

(14) 1 g of molybdenum trioxide was ground to smaller than 60 mesh, placed in a quartz tube, and it was temperature programmed to 700° C. in an ammonia gas reaction atmosphere for 1 hour, and then cooled to room temperature in an ammonia gas reaction atmosphere; wherein, the heating rate was 10° C./minute, the flux of ammonia gas was 20 mL/min;

(15) The reaction atmosphere was switched to methane and hydrogen gas, and it was temperature programmed to 700° C. for 1 hour, and then cooled to room temperature in a methane and hydrogen atmosphere; wherein the heating rate was 10° C./min, the flux of methane and hydrogen gas was 20 mL/min, the volume ratio of methane to hydrogen gas was 3:7;

(16) The reaction atmosphere was switched to an atmosphere for passivation, and it was temperature programmed to 700° C. for 1 hour, and then cooled to room temperature in the atmosphere for passivation; wherein, the heating rate was 10° C./minute, and the flux of atmosphere for passivation was 20 mL/minute. The atmosphere for passivation contained oxygen gas and argon gas, and the volume of oxygen gas accounted for 0.5% of the volume of atmosphere for passivation. Finally, 0.7 g of α-MoC.sub.1-x was obtained. The prepared support α-MoC.sub.1-x was specifically α-MoC.sub.0.8 as determined by elemental analysis.

EXAMPLE 2

Synthesis of Pt/α-MoC.SUB.0.8 .Supported Single-Atomic Dispersion Catalyst (Loaded Amount of 0.2%)

(17) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolved in 10 mL of water to prepare Pt solution; 25 μL of Pt solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 3:17), heated to 300° C. at the rate of 10° C./minute, maintained at 300° C. for one hour, and then heated to 590° C. at the rate of 10° C./min, maintained for 120 minutes. Finally, the loaded amount was determined to be about 0.2% by ICP (Inductively Coupled Plasma Spectrometer).

EXAMPLE 3

Synthesis of Pt/α-MoC.SUB.0.8 .Supported Single-Atomic Dispersion Catalyst (Loaded Amount of 0.05%)

(18) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolved in 10 mL of water to prepare Pt solution; 5 μL of Pt solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 3:17), heated to 300° C. at the rate of 10° C./min, maintained at 300° C. for 1 hour, and then heated to 590° C. at the rate of 10° C./min, maintained for 120 minutes. Finally, the loaded amount was determined to be about 0.05% by ICP.

EXAMPLE 4

Synthesis of Pt/α-MoC.SUB.0.8 .Supported Single-Atomic Dispersion Catalyst (Loaded Amount of 2%)

(19) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolved in 10 mL of water to prepare Pt solution; 150 μL of Pt solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 1:9), heated to 200° C. at the rate of 5° C./min, maintained at 200° C. for 2 hours, and then heated to 700° C. at the rate of 5° C./min, maintained for 60 minutes. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 5

Synthesis of Pd/α-MoC.SUB.0.8 .Catalyst (Loaded Amount of 2%)

(20) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of palladium chloride (precursor salt) was dissolved in 10 mL of 2 mol/L hydrochloric acid to prepare Pd solution; 8 μL of Pd solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 9:1), heated to 300° C. at the rate of 10° C./min, maintained at 300° C. for 1 hours, and then heated to 590° C. at the rate of 10° C./min, maintained for 120 minutes. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 6

Synthesis of Ru/α-MoC.SUB.0.8 .Catalyst (Loaded Amount of 2%)

(21) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of ruthenium chloride (precursor salt) was dissolved in 10 mL of water to prepare Ru solution; 10 μL of Ru solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in C.sub.2H.sub.6/H.sub.2 atmosphere (volume ratio of ethane to hydrogen gas was 3:17), heated to 300° C. at the rate of 10° C./min, maintained at 300° C. for 1 hours, and then heated to 490° C. at the rate of 10° C./min, maintained for 10 hours. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 7

Synthesis of Ni/α-MoC.SUB.0.8 .Catalyst (Loaded Amount of 2%)

(22) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of nickel nitrate was dissolved in 10 mL of water to prepare a Ni solution; 25 μL of Ni solution was added to a flask equipped with support α-MoC.sub.0.8, stirring for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 3:17), heated to 300° C. at the rate of 10° C./min, maintained at 300° C. for 1 hours, and then heated to 590° C. at the rate of 10° C./min, maintained for 120 minutes. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 8

Synthesis of Cu/α-MoC.SUB.0.8 .Catalyst (Loaded Amount of 2%)

(23) The differences between Example 8 and Example 7 were in that 1 g of cupric nitrate was dissolved in 10 mL of water to prepare Cu solution; 25 μL of Cu solution was added to a flask equipped with support α-MoC.sub.0.8 for impregnation. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 9

Synthesis of Co/α-MoC.SUB.0.8 .Catalyst (Loaded Amount of 2%)

(24) The differences between Example 9 and Example 7 were in that 1 g of cobalt nitrate was dissolved in 10 mL of water to prepare Co solution; 25 μL of Co solution was added to a flask equipped with support α-MoC.sub.0.8 for impregnation. Finally, the loaded amount was determined to be about 2% by ICP.

EXAMPLE 10

Synthesis of Pt/α-MoC.SUB.0.8 .Supported Single-Atomic Dispersion Catalyst (Loaded Amount of 10%)

(25) The support α-MoC.sub.0.8 (0.2 g) prepared in the same manner as Example 1 was placed in a flask, and 10 mL of deionized water was added to make the support completely under the liquid level. 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolved in 10 mL of water to prepare a Pt solution; 610 μL of Pt solution was added to a flask equipped with support α-MoC.sub.0.8, and stirred for 2 hours, and the water in the flask was evaporated with a rotary evaporator and then a sample obtained was placed in a lyophilizer to lyophilize overnight. The catalyst precursor was then carburized in CH.sub.4/H.sub.2 atmosphere (volume ratio of methane to hydrogen gas was 0.1:9), heated to 200° C. at the rate of 10° C./min, maintained at 200° C. for 10 hours, and then heated to 900° C. at the rate of 30° C./min, maintained for 10 minutes. Finally, the loaded amount is determined to be about 10% by ICP.

COMPARATIVE EXAMPLE 1

Synthesis of Pt/α-MoC.SUB.1-x .Catalyst (Ammonium Heptamolybdate) (Loaded Amount of 2%)

(26) 1 g of ammonium heptamolybdate was dissolved in 10 mL of deionized water, stirred until being completely dissolved, 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolved in 10 mL of water, and the aqueous solution of chloroplatinic acid was added into the ammonium molybdate solution, stirred for 2 hours until the precipitation was completed, and evaporated to dryness in an oil bath at 100° C., ground and placed in an oven at 60° C. for 3 hours. Then the catalyst precursor was placed in a muffle furnace for calcination, and it was temperature programmed to 500° C. for 120 minutes. The catalyst precursor was then carburized in 20% CH.sub.4/H.sub.2 atmosphere and it was temperature programmed to 700° C. for 120 minutes. In the catalyst prepared in this comparative example, Pt was present as dispersed nanoparticle form.

COMPARATIVE EXAMPLE 2

Synthesis of Pt/Al.SUB.2.O.SUB.3 .Catalyst (Loaded Amount of 2%)

(27) 1 g of chloroplatinic acid hexahydrate (platinum precursor salt) was dissolve in 10 mL of water. 650 μL of platinum precursor salt and 150 μL of water was mixed to form a 800 μL solution, then adding 800 μL solution into 0.8 g of Al.sub.2O.sub.3 (equal volume impregnation), stirred to dryness and placed in an oven at 60° C. for 3 hours, then the catalyst precursor was placed in a muffle furnace for calcination, and it was temperature programmed to 500° C. for 120 minutes. The catalyst precursor was then reduced in H.sub.2 atmosphere, and it was temperature programmed to 500° C. and maintained at 500° C. for 120 minutes.

COMPARATIVE EXAMPLE 3

Synthesis of Ni/Mo.SUB.2.C Catalyst (Loaded Amount of 2%)

(28) 1 g of ammonium heptamolybdate was dissolved in 10 mL of deionized water, stirred until being completely dissolved, 1 g of nickel nitrate hexahydrate (precursor salt) was dissolved in 10 mL of water, and 25 μL of aqueous solution of nickel nitrate was added to the ammonium heptamolybdate solution, and stirred for 2 hours until the precipitation was completed, evaporated to dryness in an oil bath at 100° C., ground and placed in an oven at 60° C. for 3 hours, and then the catalyst precursor was placed in a muffle furnace for calcination, and it was temperature programmed to 500° C. at a rate of 10° C./min, maintained for 120 minutes. The catalyst precursor was then carburized in 20% CH.sub.4/H.sub.2 atmosphere, heated to 300° C. at a rate of 5° C./min, and then raised to 700° C. at a rate of 1° C./min, maintained for 120 minutes. For the synthesis method, see Ma, Y, et al., International Journal of Hydrogen Energy, 2014. 39(1): p. 258-266.

COMPARATIVE EXAMPLE 4

Synthesis of Ni/Al.SUB.2.O.SUB.3 .Catalyst (Loaded Amount 2%)

(29) 1 g of nickel nitrate hexahydrate was dissolved in 10 mL of water, 100 μL of nickel nitrate was added into 0.8 g of Al.sub.2O.sub.3, stirred to dryness and placed in an oven at 60° C. for 3 hours, and then the catalyst precursor was placed in a muffle furnace for calcination. It was temperature programmed to 500° C. at a rate of 10° C./min, maintained for 120 minutes. The catalyst precursor was reduced in an atmosphere of H.sub.2, and the temperature was heated to 500° C. at a rate of 5° C./min and maintained at 500° C. for 120 minutes.

COMPARATIVE EXAMPLE 5

(30) Preparing Pt/α-MoC.sub.1-x supported catalyst as described in Example 1 of the Chinese Patent Application No. 201510053793.8, with the title of “Pt/α-MoC.sub.1-x supported catalyst, synthesis method and application thereof”, wherein Pt was dispersed on α-MoC.sub.1-x support in a layer form.

(31) Characterization and Testing

(32) XRD Characterization

(33) The support α-MoC.sub.0.8 prepared in Example 1 and the catalysts prepared in Examples 2, 5, 6, 7, 8 and 9 were characterized by XRD to observe the phase structure thereof; the XRD sample was prepared as follows: the above carburized catalyst was passivated with a passivation gas of 0.5% O.sub.2/Ar for 8 hours, and ground for using in an XRD test. The results are shown in FIG. 1. It can be seen from FIG. 1 that the support α-MoC.sub.0.8 is an α phase, and the metals in Examples 2, 5, 6, 7, 8 and 9 are not present in the form of dispersed nanoparticle.

(34) Proof of Single Atom of Pt in Pt/α-MoC.sub.0.8 Supported Single-Atomic Dispersion Catalyst Prepared in Example 2

(35) Transmission Electron Microscopy Characterization

(36) The preparation method of the transmission electron microscope sample was as follows: the catalyst obtained in Example 2 and the catalyst of Example 2 after performing the methanol aqueous phase hydrogen production reaction were placed in a glove box respectively; after grinding, the solid was introduced into deoxygenated anhydrous ethanol to disperse; a few drops of the dispersed droplets were added dropwise on the ultrathin carbon film for transmission electron microscopy, air-dried, and then sent into the transmission electron microscope for testing. The results are shown in FIGS. 2A and 2B, wherein the catalyst obtained in Example 2 before the reaction is shown in FIG. 2A, while the catalyst after the reaction is shown in FIG. 2B. It can be seen from FIG. 2A and FIG. 2B that the Pt atoms are dispersed on the α-MoC.sub.0.8 support in the form of single atom (Pt atoms are the dots in circle in the figure) no matter before or after the reaction. This indicates that the catalyst prepared in Example 2 has a good stability and does not agglomerate after the catalytic reaction.

(37) In order to further demonstrate that the Pt element in the catalyst prepared in Example 2 were all dispersed on the α-MoC.sub.0.8 support in the form of single atom, the catalyst obtained in Example 2 and the catalyst of Example 2 after performing the methanol aqueous phase hydrogen production reaction were respectively characterized by X-ray absorption fine structure spectrum (XAFS), and their X-ray absorption fine structure spectrum were obtained, and the extended edge was analyzed and fitted (EXAFS). XAFS is a powerful tool for depicting bulk phase structure, it adjusts X-ray energy to be consistent with the elements of the studied sample, and then monitors the functional relationship between the amount of x-rays absorbed and their energy. With sufficient accuracy, the spectrum will exhibit small oscillations, which is the result of the local environment's effect on the basic absorption probability of the target element. By analyzing and fitting the extended edge (EXAFS), the distance between absorbed atoms and neighbor atoms, the number and type of these atoms and the oxidation state of the absorbed elements can be obtained, which are the parameters for determining local structure. The results are shown in FIG. 3 and Table 1, wherein (a) in FIG. 3 is an EXAFS fitting graph of the Pt L3 absorption edge in the catalyst before the reaction; (b) in FIG. 3 is the EXAFS fitting graph of the Pt L3 absorption edge in the catalyst after the reaction; (c) in FIG. 3 is the XANS graph of the Pt L3 absorption edge in the catalyst before and after the reaction; and (d) in FIG. 3 is the XANS graph of the Mo absorption K edge in the catalyst before and after the reaction.

(38) TABLE-US-00001 TABLE 1 EXAFS Data Fitting of Pt L3 Absorption Edge of Catalyst After the Reaction or Before the Reaction Coordination Bond Coordination Structural Catalyst Shell Length (Å) Number E0 Displacement (ev) Disorder Before the Pt—Pt — — 5.9 — reaction Pt—Mo  2.5 +/− 0.01 6.8 +/− 1.0 0.015 After the Pt—Pt — — 5.9 — reaction Pt—Mo 2.85 +/− 0.01 6.8 +/− 1.0 0.013

(39) It can be seen from Table 1 that the coordination number (C.N..sub.Pt—Pt) of Pt—Pt is 0, that is, there is no another Pt atom in the spatial range of 0.3 nm around Pt in the entire catalyst structure, thereby demonstrating microscopically and macroscopically that Pt in the catalyst prepared in Example 2 is single-atomic dispersed.

(40) Proof of Single Atom of Pt in 0.05% Pt/α-MoC.sub.0.8 Supported Single-Atomic Dispersion Catalyst Prepared in Example 3

(41) The catalyst prepared in Example 3 was characterized by transmission electron microscopy, and the results are shown in FIG. 4. As can be seen from FIG. 4, Pt atoms are all dispersed on the α-MoC.sub.0.8 support in the form of single atom.

(42) Proof of Single Atom of Pt in 2% Pt/α-MoC.sub.0.8 Supported Single-Atomic Dispersion Catalyst Prepared in Example 4

(43) The catalyst prepared in Example 4 was characterized by transmission electron microscopy, and the results are shown in FIG. 5 and Table 2. As can be seen from FIG. 5, Pt atoms are uniformly present on the α-MoC.sub.0.8 support in the form of single atom (as shown in the circle), the Pt particles are hardly observed.

(44) Combined with EXAFS fitting analysis, the amount of Pt single atom is about 90% of the total Pt mass loaded on the support.

(45) TABLE-US-00002 TABLE 2 EXAFS Data Fitting of Pt L3 Absorption Edge of 2% Pt/α-MoC.sub.0.8 Supported Single-Atomic Dispersion Catalyst Coordination Bond Coordination Structural Catalyst Shell Length Å Number E0 Displacement (eV) Disorder 2% Pt/α-MoC.sub.0.8 Pt—Pt 2.78 +/− 0.01 4.8 +/− 0.7 6.4 0.005 Pt—Mo 2.78 +/− 0.01 3.2 +/− 0.7 0.006

(46) Proof of Single Atom of Pt in 10% Pt/α-MoC.sub.0.8 Supported Single-Atomic Dispersion Catalyst Prepared in Example 10

(47) The catalyst prepared in Example 10 was characterized by transmission electron microscopy. The results are shown in FIG. 6 and Table 3. As can be seen from the graph a in FIG. 6, when the loaded amount reaches 10%, more Pt particles appear on the catalyst. As can be seen from the graph b in FIG. 6, there is a part of the Pt single atom remaining on the catalyst. Also combined with XAFS fitting data, the coordination number of Pt—Mo is 2.7, which is mainly contributed by the interaction between Pt single atom and the support molybdenum carbide. The coordination number of Pt—Pt is 5.2, which is mainly contributed by Pt particles. The amount of Pt single atom is about 10% of the total Pt mass loaded on the support.

(48) TABLE-US-00003 TABLE 3 EXAFS data fitting of Pt L3 edge of 10% Pt/α-MoC.sub.0.8 supported single-atomic dispersion catalyst Coordination Bond Coordination Structural Catalyst Shell Length Å Number E0 Displacement (eV) Disorder 10% Pt/α-MoC.sub.0.8 Pt—Pt 2.75 +/− 0.01 5.2 +/− 1.0 5.9 0.005 Pt—Mo 2.75 +/− 0.01 2.7 +/− 0.7 0.003

(49) Catalytic Performance Test in the Hydrogen Production of Alcohol Aqueous Phase Reforming

(50) The supported catalysts prepared in Examples 2-9 and Comparative Examples 1-5 were used in the methanol aqueous phase reforming reaction under the following conditions: a closed system reaction, in which a certain proportion of methanol and water were added to the reaction system (the reaction was carried out according to the optimal ratio of catalyst), and the reaction was carried out under 2 MPa N.sub.2 (10% Ar as an internal standard) protective gas, after the temperature was cooled to room temperature, the gas phase product was detected by gas chromatography. The reaction performance of each catalyst is shown in Table 4 below.

(51) Wherein activity evaluation conditions of Examples 2-6, Comparative Example 1-2 and Comparative Example 5 were as follows: n (methanol):n (water)=1:1, reaction temperature was 190° C., and the reaction was carried out for 1 hour, and the activity was represented by ATOF (Aver TOF; average conversion frequency: moles of reactants converted on metal per mole in one hour).

(52) Activity evaluation conditions of Examples 7-9, Comparative Example 3-4 were as follows: n (methanol):n (water)=1:1, reaction temperature was 240° C., the reaction was carried out for 3 hour, and the activity was represented by μmol/g/s.

(53) TABLE-US-00004 TABLE 4 Comparison of catalytic performance of the catalysts in hydrogen production of alcohol aqueous phase reforming Temperature ATOF Catalyst (° C.) (h.sup.−1) μmol/g/s n.sub.CO/n.sub.H2 % Example 1 240 — 1.2 0.83 α-MoC.sub.0.8 Example 2 190 22557 93.2 0.14 0.2% Pt/α-MoC.sub.0.8 Example 3 190 23150 16.4 0.09 0.05% Pt/α-MoC.sub.0.8 Example 4 190 5025 143.2 0.06 2% Pt/α-MoC.sub.0.8 Example 5 190 2325 121.9 0.07 2% Pd/α-MoC.sub.0.8 Example 6 190 2130 117.2 0.05 2% Ru/α-MoC.sub.0.8 Comparative Example 1 190 852 24.3 0.12 2% Pt/α-MoC.sub.1−x Comparative Example 2 190 103 2.9 0.07 2% Pt/Al.sub.2O.sub.3 Comparative Example 5 190 8630 201 0.09  Pt/α-MoC.sub.1−x Example 7 240 95.7 0.71 Ni/α-MoC.sub.0.8 Example 8 240 1.81 0.07 Cu/α-MoC.sub.0.8 Example 9 240 1.4 0.07 Co/α-MoC.sub.0.8 Comparative Example 3 240 18.5 1.7 Ni/Mo.sub.2C Comparative Example 4 240 7.8 26.8 Ni/Al.sub.2O.sub.3

(54) It can be seen from Table 4, the catalytic activity of the catalyst prepared in each example of the present application is significantly higher than that of the catalyst prepared in the comparative example. Meanwhile, the catalyst of the present application not only has a relatively high hydrogen production rate and low CO selectivity, but also is far lower than the tolerance of the high temperature hydrogen fuel cell to CO, and it overcomes the weakness of the low catalytic activity and high CO selectivity of the Pt catalyst loaded by the oxide support; especially the catalyst prepared in Examples 2 and 3, its TOF activity is as high as 22557 h.sup.−1 and 23150 h.sup.−1. In addition, the catalytic reaction was repeated using the catalyst of Example 2 (the reaction conditions were the same as that in Table 4), after each reaction, the composition of the gas in the reaction was detected by gas chromatography, and the amount of the substance of each component was determined by the content of the internal standard, and the reaction rate was calculated finally. The result is shown in FIG. 7, it can be seen from FIG. 7 that the catalyst prepared by the present application has good stability and can be used repeatedly for the catalytic reaction multiple times.

(55) In order to investigate the optimum reaction temperature of the Ni\Cu\Co catalyst provided by the present application, specifically, the catalysts prepared in Example 7 and Comparative Example 3 were taken as an example, the catalytic reaction was carried out at different temperatures under the conditions of n(methanol):n (water)=1:1 and performing reaction for 3 hours. The result is shown in FIG. 8, it can be seen from FIG. 8 that the activity of Ni/α-MoC.sub.0.8 prepared in Example 7 is increased significantly in this reaction as the temperature increased and the activity is the highest at 240° C.

(56) In order to investigate the optimum alcohol-water ratio of the catalyst provided by the present application, the alcohol-water ratio optimization test was carried out by taking Example 2 and Example 7 as an example. Specifically, the reaction temperature of Example 2 was 190° C., and the reaction time was 1 hour; the reaction temperature of Example 7 was 240° C. and the reaction was carried out for 3 hours. The results are shown in FIG. 9 and FIG. 10, it can be seen that the optimum alcohol-water ratio of Example 2 and Example 7 is n (methanol):n (water)=1:1.

(57) Each of the catalysts prepared in the present application not only has a remarkable catalytic effect on methanol, but also has good catalytic performance on other alcohols. Table 5 shows the results of the hydrogen production of aqueous phase reforming of ethanol, ethylene glycol, and glycerin using the examples of the present application.

(58) Specifically, the supported catalysts prepared in Example 2 and Example 7 are used in the aqueous alcohol reforming reaction under the following conditions: a closed system reaction, in which a certain proportion of alcohol (ethanol, ethylene glycol, and glycerin) and water was added to the reaction system, and the reaction was carried out under 2 MPa N.sub.2 (10% Ar as an internal standard) protective gas, after the temperature was cooled to room temperature, the gas phase product was detected by gas chromatography. The reaction performance of each catalyst is shown in Table 5 below.

(59) Wherein the activity evaluation conditions of Example 2: n (alcohol):n (water)=1:1, the reaction temperature was 210° C., and the reaction was carried out for 1 hour, and the activity was represented by ATOF.

(60) The activity evaluation conditions of Example 7: n (alcohol):n (water)=1:1, the reaction temperature was 210° C., and the reaction was carried out for 3 hour, and the activity was represented by μmol/g/s.

(61) TABLE-US-00005 TABLE 5 The reaction performance of the catalysts of Example 2 and Example 7 for catalyzing the hydrogen production of aqueous phase alcohol reforming Temperature ATOF nCO/ Catalyst Alcohol (° C.) (h.sup.−1) μmol/g/s nH.sub.2 % Pt/α-MoC.sub.0.8 Ethanol 210 1275 — Pt/α-MoC.sub.0.8 Glycerin 210 874 0.12 Pt/α-MoC.sub.0.8 ethylene 210 608 0.07 glycol Ni/α-MoC.sub.0.8 Ethanol 240 50.2 0.5 Ni/α-MoC.sub.0.8 Glycerin 240 28.4 0.9 Ni/α-MoC.sub.0.8 ethylene 240 28.7 0.7 glycol

(62) As can be seen from Table 5, in addition to methanol, the catalyst provided by the present application has excellent catalytic properties for other alcohols.

(63) In summary, the catalyst prepared by the preparation method of the metal/α-MoC.sub.1-x supported single-atomic dispersion catalyst provided by the present application, in which the metal is uniformly dispersed on the support α-MoC.sub.1-x in single atom form, can improve the coverage of “—OH” on the catalyst surface more effectively, and the “—OH” is favorable for the metal to catalyze the “—CH” cleavage so that promotes the alcohol reforming reaction and inhibits the decomposition reaction.

(64) The above description is only the preferred example of the present application, and is not intended to limit the present application. Any modifications, equivalent substitutions, improvements, etc., which are made within the spirit and principles of the present application, should be included within the scope of protection of the present application.