CN113275019B - Magnetic nickel-cobalt oxide supported gold catalyst, preparation method and application thereof, and preparation method of 2,5-furandicarboxylic acid - Google Patents

Magnetic nickel-cobalt oxide supported gold catalyst, preparation method and application thereof, and preparation method of 2,5-furandicarboxylic acid Download PDF

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CN113275019B
CN113275019B CN202110622607.3A CN202110622607A CN113275019B CN 113275019 B CN113275019 B CN 113275019B CN 202110622607 A CN202110622607 A CN 202110622607A CN 113275019 B CN113275019 B CN 113275019B
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方文浩
张�浩
曹秋娥
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Yunnan University YNU
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Abstract

The invention provides a magnetic nickel-cobalt oxide supported gold catalyst, a preparation method and application thereof, and a preparation method of 2,5-furandicarboxylic acid, and belongs to the technical field of catalysts. The magnetic nickel cobalt oxide supported gold catalyst provided by the invention comprises a magnetic nickel cobalt oxide carrier and gold nanoparticles supported on the magnetic nickel cobalt oxide carrier; the chemical composition of the magnetic nickel-cobalt oxide carrier is CoNi x O y Wherein x is 1 to 5; y is such that CoNi is satisfied x O y The number of oxygen atoms in the valence state zero. The magnetic nickel-cobalt oxide supported gold catalyst provided by the invention has high catalytic activity for preparing 2,5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural, high selectivity for a target product 2,5-furandicarboxylic acid, good stability, high repeated utilization rate and high efficiency, is specific, green and environment-friendly, and can realize separation of the catalyst and the product in a simple physical magnetic separation manner.

Description

Magnetic nickel-cobalt oxide supported gold catalyst, preparation method and application thereof, and preparation method of 2,5-furandicarboxylic acid
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a magnetic nickel-cobalt oxide supported gold catalyst, a preparation method and application thereof, and a preparation method of 2,5-furandicarboxylic acid.
Background
The development of the traditional chemical industry depends heavily on petrochemical products extracted from fossil energy, and with the gradual exhaustion of the petrochemical energy and the serious environmental pollution problem brought by the petrochemical energy, people are prompted to find new renewable green chemical energy. According to the definition of the international energy agency, biomass refers to various organisms formed in plants through photosynthesis, and has the characteristics of renewability, low pollution, wide distribution, rich resources, neutral carbon and the like. The biomass energy is the fourth largest energy after coal, petroleum and natural gas, and plays an important role in the whole energy system. Since the 70 s of the 20 th century, the high-efficiency development and utilization of biomass has been particularly emphasized in various countries, and research and development of biomass application technology have been actively conducted and many research results have been obtained. 5-hydroxymethyl furfural is a basic structural unit of lignocellulose biomass, is one of the most important biomass platform molecules, and can be widely applied to preparation of functional polyester, liquid fuel and various fine chemicals.
2,5-furandicarboxylic acid is a basic raw material with wide application and good stability, and is considered as one of 12 high-value-added compounds obtained from biomass by the U.S. department of energy as early as 2004. The 2,5-furandicarboxylic acid has a structure similar to that of terephthalic acid (synthetic monomer of PET plastic), and can be used as a green renewable substitute chemical for producing bio-based plastic. Polyethylene 2,5-furancarboxylic acid ester (PEF plastic for short) obtained by 2,5-furandicarboxylic acid polymerization can be degraded and recycled, has more excellent performance than PET plastic, can widely replace PET, and is applied to various aspects of chemical industry and production life. 2,5-furandicarboxylic acid can be prepared by selective oxidation of 5-hydroxymethylfurfural, which has the following reaction route:
Figure GDA0003842304280000021
a commonly used gold-based catalyst for preparing 2,5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural takes a carbon material or hydrotalcite as a carrier and takes gold nanoparticles as an active component. However, the catalyst with the gold nanoparticles loaded on the carbon material has low catalytic activity, the selectivity of the product is poor, and more byproducts are generated; the hydrotalcite-loaded gold catalyst has good catalytic activity and good product selectivity, but the catalyst has extremely poor stability and is difficult to reuse.
Disclosure of Invention
In view of the above, the invention aims to provide a magnetic nickel-cobalt oxide supported gold catalyst, and a preparation method and an application thereof, and the magnetic nickel-cobalt oxide supported gold catalyst provided by the invention has the advantages of high catalytic activity, good stability, high product selectivity and easiness in recovery in the preparation of 2,5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a magnetic nickel cobalt oxide supported gold catalyst which comprises a magnetic nickel cobalt oxide carrier and gold nanoparticles supported on the magnetic nickel cobalt oxide carrier.
The chemical composition of the magnetic nickel cobalt oxide carrier is CoNi x O y Wherein x is 1-5,y satisfies CoNi x O y The number of oxygen atoms of which the valence is zero.
Preferably, the loading of the gold nanoparticles is less than or equal to 10wt%.
Preferably, the average particle size of the gold nanoparticles is 2.2 +/-0.2 nm;
the average particle size of the magnetic nickel-cobalt oxide supported gold catalyst is 20 +/-5 nm.
The invention provides a preparation method of a magnetic nickel cobalt oxide supported gold catalyst in the technical scheme, which comprises the following steps:
mixing a water-soluble cobalt precursor, a precipitator and water, and then sequentially carrying out hydrothermal reaction, first roasting and hydrogen reduction reaction to obtain magnetic zero-valent cobalt;
mixing the magnetic zero-valent cobalt, a water-soluble nickel precursor, water-soluble carbonate and water, and sequentially performing precipitation and second roasting to obtain a magnetic nickel-cobalt oxide carrier;
and mixing a water-soluble gold precursor, polyvinylpyrrolidone, the magnetic nickel-cobalt oxide carrier, borohydride and water, and carrying out reduction reaction to obtain the magnetic nickel-cobalt oxide supported gold catalyst.
Preferably, the molar ratio of the water-soluble cobalt precursor to the precipitant is 1: (1-2).
Preferably, the temperature of the hydrothermal reaction is 90-180 ℃ and the time is 2-8 h;
the temperature of the first roasting is 300-600 ℃, and the time is 3-5 h;
the temperature of the hydrogen reduction reaction is 250-450 ℃, and the time is 0.5-2 h.
Preferably, the molar ratio of the magnetic zero-valent cobalt to the water-soluble nickel precursor to the water-soluble carbonate is 1: (1-5): (0.5-2.5);
the mol ratio of the water-soluble nickel precursor to the water-soluble carbonate is constant (0.5-1.5): 1;
the temperature of the second roasting is that the temperature of the precipitation is 300-600 ℃, and the time is 2-5 h.
Preferably, the mass ratio of the water-soluble gold precursor to the polyvinylpyrrolidone to the borohydride salt is 1: (2-5): (1-10);
the mass ratio of the water-soluble gold precursor to the magnetic cobalt-nickel composite oxide is less than or equal to 0.1.
The temperature of the reduction reaction is 25-50 ℃ and the time is 1-4 h.
The invention provides an application of the magnetic nickel cobalt oxide supported gold catalyst in the technical scheme or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method in the technical scheme in preparation of 2,5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural oxidation.
The invention also provides a preparation method of 2,5-furandicarboxylic acid, which comprises the following steps:
mixing 5-hydroxymethylfurfural, a magnetic nickel-cobalt oxide supported gold catalyst and water, and introducing oxygen to perform an oxidation reaction to obtain 2,5-furandicarboxylic acid;
the magnetic nickel cobalt oxide supported gold catalyst is the magnetic nickel cobalt oxide supported gold catalyst in the technical scheme or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method in the technical scheme.
The invention provides a magnetic nickel cobalt oxide supported gold catalyst, which comprises a magnetic nickel cobalt oxide carrier and gold nanoparticles supported on the magnetic nickel cobalt oxide carrier; the chemical composition of the magnetic nickel-cobalt oxide carrier is CoNi x O y Wherein, 1 is less than or equal to<x is not more than 5,y is CoNi x O y The number of oxygen atoms of which the valence is zero.
The invention provides a magnetic nickel-cobalt oxide supported gold catalyst (Au-CoNi) x O y ) Has the following beneficial effects: in the magnetic nickel cobalt oxide supported gold catalyst provided by the invention, the surface of the magnetic nickel cobalt oxide carrier has rich oxygen holes and active oxygen species, so that the adsorption and activation of molecular oxygen are facilitated, and gold nanoparticlesThe particles are beneficial to adsorbing and activating 5-hydroxymethylfurfural substrate molecules, water is used as a solvent, oxygen is used as an oxidant under the synergistic effect of the magnetic nickel-cobalt oxide carrier and the gold nanoparticles, the 5-hydroxymethylfurfural can be efficiently and specifically converted into 2,5-furandicarboxylic acid, the catalytic activity is high, the conversion rate of the 5-hydroxymethylfurfural is high, and the selectivity and the yield of 2,5-furandicarboxylic acid are high. The magnetic nickel-cobalt oxide supported gold catalyst provided by the invention does not need to be added with any corrosive acid solution in the reaction process of catalyzing 5-hydroxymethylfurfural to oxidize and prepare 2,5-furandicarboxylic acid, does not generate acid-base substances and toxic byproducts, and is safe and environment-friendly; the magnetic nickel-cobalt oxide supported gold catalyst provided by the invention has strong magnetism, can be quickly and thoroughly physically separated from a reaction liquid for preparing 2,5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural through an external magnetic field, can be efficiently recycled without using any chemical reagent and any extra energy, and reduces the pollution to the environment.
As shown in the results of the examples, when the oxidation temperature of the magnetic nickel cobalt oxide supported gold catalyst provided by the present invention is 120 ℃, the oxygen pressure is 10bar, and the molar ratio of 5-hydroxymethylfurfural to gold in the magnetic nickel cobalt oxide supported gold catalyst is 100, the conversion rate of 5-hydroxymethylfurfural is up to 100%, the yield of 2,5-furandicarboxylic acid is up to 100%, and the selectivity of 2,5-furandicarboxylic acid is up to 100%. The magnetic nickel-cobalt oxide supported gold catalyst provided by the invention has excellent catalytic activity, extremely high selectivity on a target product 2,5-furandicarboxylic acid, excellent stability, excellent catalytic activity after 5 times of recycling, separation of the catalyst and the product can be realized through a simple physical magnetic separation mode, the repeated utilization rate of the catalyst is high, and the magnetic nickel-cobalt oxide supported gold catalyst is an efficient, specific, green and environment-friendly catalyst.
The invention provides a preparation method of the magnetic nickel-cobalt oxide supported gold catalyst in the technical scheme. The magnetic nickel-cobalt oxide carrier prepared by the step method has the characteristic of magnetic response, the catalyst can be recycled by a simple physical magnetic separation process, the cost and the difficulty of separating products and recycling the catalyst are reduced, and the magnetic nickel-cobalt oxide carrier has wide application prospect; the reaction raw materials are cheap and easy to obtain, the preparation cost is low, the preparation method is simple to operate, and the method is suitable for industrial production.
The invention also provides a preparation method of 2,5-furandicarboxylic acid. The magnetic nickel cobalt oxide supported gold catalyst is used as the catalyst, the conversion rate of 5-hydroxymethylfurfural is high, and the selectivity and the yield of 2,5-furandicarboxylic acid are high; in addition, water is used as a solvent, oxygen is used as an oxidant, an additional acid-base additive is not required to be added in the reaction process, the pollution to the environment in the reaction process is small, and the corrosion and the loss to reaction equipment are small.
Drawings
FIG. 1 is a transmission electron microscope image of the magnetic nickel cobalt oxide supported gold catalyst prepared in example 1 at a scale of 200 nm;
FIG. 2 is a transmission electron microscope image of the magnetic Ni-Co oxide supported Au catalyst prepared in example 1 under a scale of 10nm, wherein an interpolation graph is a statistical result graph of Au particle size;
fig. 3 is an XRD test pattern of each product during the preparation of the magnetic nickel cobalt oxide support of example 1;
FIG. 4 is an XRD test pattern of magnetic nickel cobalt oxide supports of different Co/Ni ratios prepared in examples 1-3;
FIG. 5 is a graph of the magnetic test results of the magnetic nickel cobalt oxide supported gold catalyst prepared in example 1 after oxidation with 5-hydroxymethylfurfural to produce 2,5-furandicarboxylic acid;
fig. 6 is a graph showing the results of a cycle test of the magnetic nickel cobalt oxide supported gold catalyst prepared in example 1.
Detailed Description
The invention provides a magnetic nickel cobalt oxide supported gold catalyst which comprises a magnetic nickel cobalt oxide carrier and gold nanoparticles supported on the magnetic nickel cobalt oxide carrier.
In the invention, the chemical composition of the magnetic nickel cobalt oxide carrier is CoNi x O y Wherein x is 1 to 5; y is such that CoNi is satisfied x O y The valence being zeroThe number of oxygen atoms.
In the present invention, x is preferably 1, 2, 3, 4 or 5, more preferably 1, 3 or 5.
In the present invention, the gold nanoparticle loading is preferably 10wt% or less, more preferably 0.01 to 10wt%, most preferably 1 to 5wt%.
In the present invention, the average particle diameter of the gold nanoparticles is preferably 2.2nm. In the present invention, the magnetic nickel cobalt oxide supported gold catalyst preferably has an average particle diameter of 20nm.
The magnetic nickel-cobalt oxide supported gold catalyst provided by the invention is low in load, the gold nanoparticles are small in particle size, uniform and highly dispersed and supported on the magnetic nickel-cobalt oxide carrier, the catalytic activity of the catalyst is improved, the dosage is small in the process of catalyzing 5-hydroxymethylfurfural to prepare 2,5-furandicarboxylic acid through oxidation, and the cost of the catalyst is low.
The invention provides a preparation method of the magnetic nickel cobalt oxide supported gold catalyst, which comprises the following steps:
mixing a water-soluble cobalt precursor, a precipitator and water, and then sequentially carrying out hydrothermal reaction, first roasting and hydrogen reduction reaction to obtain a zero-valent cobalt-cobalt oxide magnetic mixture;
mixing the zero-valent cobalt-cobalt oxide magnetic mixture, a water-soluble nickel precursor, water-soluble carbonate and water, and sequentially carrying out precipitation and second roasting to obtain a magnetic nickel-cobalt oxide carrier;
and mixing a water-soluble gold precursor, polyvinylpyrrolidone, the magnetic nickel-cobalt oxide carrier, borohydride and water, and carrying out reduction reaction to obtain the magnetic nickel-cobalt oxide supported gold catalyst.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing a water-soluble cobalt precursor, a precipitator and water, and then sequentially carrying out hydrothermal reaction, first roasting and hydrogen reduction reaction to obtain the magnetic zero-valent cobalt.
In the invention, the water-soluble cobalt precursor is preferably a water-soluble cobalt salt, and the water-soluble cobalt salt preferably comprises one or more of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt bromide. In the present invention, the precipitant preferably includes one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, and triethylamine. In the present invention, the molar ratio of the water-soluble cobalt precursor to the precipitant is preferably 1: (1-2), more preferably 1: (1.2 to 1.8), most preferably 1: (1.5-1.6). In the present invention, the water is preferably deionized water; the ratio of the amount of cobalt species in the water-soluble cobalt salt to the volume of water is preferably 1mmol: (5 to 20) mL, more preferably 1mmol: (10-15) mL, most preferably 1mmol: (12-13) mL.
In the present invention, the mixing is preferably performed by stirring; the stirring and mixing speed is preferably 400 to 600rpm, more preferably 500 to 550rpm; the stirring and mixing time is preferably 1-2 h, and more preferably 1.5h; the mixing is preferably carried out in a hydrothermal kettle.
In the present invention, the temperature of the hydrothermal reaction is preferably 90 to 180 ℃, more preferably 100 to 150 ℃, and most preferably 110 to 130 ℃; the hydrothermal reaction time is preferably 2 to 8 hours, more preferably 3 to 6 hours, and most preferably 4 to 5 hours. In the present invention, the hydrothermal reaction is preferably carried out in a hydrothermal reactor.
In the invention, when the precipitator is urea, the urea precipitator is decomposed at high temperature in the water phase to generate CO in the hydrothermal reaction process 3 2- ，CO 3 2- And Co 2+ Reaction to pink CoCO 3 Precipitate, the specific reaction in the process is:
CO(NH 2 ) 2 +3H 2 O→2NH 4 + +CO 2 +2OH -
CO 2 +2OH - →CO 3 2- +H 2 O
Co 2+ +CO 3 2- →CoCO 3
in the present invention, when the precipitant is sodium hydroxide and/or potassium hydroxide, the specific reaction occurring during the hydrothermal reaction is as follows:
NaOH→Na + +OH - and/or KOH → K + +OH -
Co 2+ +2OH - →Co(OH) 2
In the present invention, when the precipitant is sodium bicarbonate and/or sodium carbonate, the specific reaction occurring during the hydrothermal reaction is as follows:
Na 2 CO 3 →2Na + +CO 3 2- or K 2 CO 3 →2K + +CO 3 2-
Co 2+ +CO 3 2- →CoCO 3
In the present invention, when the precipitant is Triethylamine (TEA), the specific reaction occurring during the hydrothermal reaction is as follows:
TEA+Co 2+ →Co 2+ -TEA (Complex precipitated)
After the hydrothermal reaction, the method preferably further comprises cooling a system of the hydrothermal reaction to room temperature, performing solid-liquid separation, drying an obtained solid product, and then performing the first roasting. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used, specifically, natural cooling. The solid-liquid separation method of the present invention is not particularly limited, and a cooling method known to those skilled in the art, such as filtration, may be employed. In the present invention, the drying temperature is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the drying time is preferably 12 to 14 hours, and more preferably 13 hours; the drying is preferably carried out in an oven.
In the present invention, the temperature of the first roasting is preferably 300 to 600 ℃, more preferably 350 to 550 ℃, and most preferably 400 to 500 ℃; the first roasting time is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours, and most preferably 4 hours; in the first roasting process, coCO 3 Decomposing at high temperature to obtain black Co 3 O 4 And (3) powder.
In the present invention, the temperature of the hydrogen reduction reaction is preferably 250 to 450 ℃, more preferably 300 to 400 ℃, and most preferably 350 ℃; the time of the hydrogen reduction reaction is preferably 0.5 to 2 hours, and more preferably 1 to 1.5 hours; the pressure of hydrogen is preferably 0 to 1MPa, more preferably 0.1 to 0.5MPa, most preferably 0.2 to 0.3MPa; during the hydrogen reduction reaction, co 3 O 4 Reduced to magnetic zero-valent cobalt.
After the magnetic zero-valent cobalt is obtained, the magnetic zero-valent cobalt, the water-soluble nickel precursor, the water-soluble carbonate and water are mixed, and precipitation and secondary roasting are sequentially carried out to obtain the magnetic nickel-cobalt oxide carrier.
In the invention, the water-soluble nickel precursor preferably comprises one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel bromide. In the present invention, the water-soluble carbonate preferably includes sodium carbonate, potassium carbonate, sodium bicarbonate. In the present invention, the molar ratio of the magnetic zero-valent precursor to the water-soluble nickel precursor is preferably 1: (1 to 5), more preferably 1: (2-4), most preferably 1:3. In the present invention, the amount of the water-soluble carbonate is not particularly limited, and the pH of the system may be adjusted to 7 to 11, more preferably 8 to 10, and still more preferably 9.
In the invention, the mixing of the magnetic mixture of zero-valent cobalt and cobalt oxide, the water-soluble nickel precursor, the water-soluble carbonate and the water preferably comprises ultrasonic mixing of the magnetic mixture of zero-valent cobalt and cobalt oxide and water, adding the water-soluble nickel precursor into the obtained dispersion liquid, stirring and mixing, adding the water-soluble carbonate into the obtained mixed liquid, stirring and mixing; the time of ultrasonic mixing is preferably 5 to 20min, and more preferably 10 to 15min; the power of ultrasonic mixing is not specially limited, and the magnetic zero-valent cobalt can be uniformly dispersed in water; the time for adding the water-soluble nickel precursor, stirring and mixing is preferably 5-30 min, and more preferably 10-20 min; the stirring and mixing speed is not specially limited, and the raw materials can be uniformly mixed; the time for adding the water-soluble carbonate to stir and mix is preferably 5 to 30min, and more preferably 10 to 20min; the stirring and mixing speed is not particularly limited, and the raw materials can be uniformly mixed.
In the present invention, the temperature of the precipitation is preferably 25 to 60 ℃, more preferably 30 to 45 ℃, and most preferably 35 to 40 ℃; the settling time is preferably 1 to 4 hours, more preferably 2 to 3 hours, and most preferably 2.5 hours; the precipitation is preferably carried out under stirring; the stirring speed is not particularly limited in the invention, and the stirring speed known to those skilled in the art can be adopted; in the precipitation process, the water-soluble nickel precursor reacts with carbonate to generate nickel carbonate precipitate.
After the precipitation, the invention preferably further comprises the steps of carrying out solid-liquid separation on the precipitated system, and sequentially washing and drying the obtained solid products to obtain the magnetic nickel-cobalt oxide carrier. The solid-liquid separation mode is not particularly limited, and the solid-liquid separation mode known to those skilled in the art can be adopted, such as filtration; the number of times of the water washing is not particularly limited, and the unreacted water-soluble nickel precursor and the water-soluble carbonate can be washed clean. In the present invention, the drying temperature is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the drying time is preferably 12 to 14 hours, and more preferably 13 hours; the drying is preferably carried out in an oven.
In the present invention, the temperature of the second roasting is preferably 300 to 600 ℃, more preferably 350 to 550 ℃, and most preferably 400 to 500 ℃; the time of the second roasting is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 3 hours; the atmosphere of the second roasting is preferably air; in the second roasting process, the magnetic zero-valent cobalt reacts with oxygen in the air to generate high-valence cobalt oxide; decomposition of nickel carbonate at high temperature to form CO 2 And NiO, the cobalt oxide and NiO forming a nickel-cobalt composite oxide (i.e., a magnetic nickel-cobalt oxide support).
After the magnetic nickel cobalt oxide carrier is obtained, the invention mixes the water-soluble gold precursor, polyvinylpyrrolidone, the magnetic nickel cobalt oxide carrier, borohydride and water, and carries out reduction reaction to obtain the magnetic nickel cobalt oxide supported gold catalyst.
In the present invention, the water-soluble gold precursor preferably includes chloroauric acid and/or sodium chloroaurate. In the present invention, the borohydride salt preferably includes sodium borohydride and/or potassium borohydride. In the present invention, the mass ratio of the water-soluble gold precursor, polyvinylpyrrolidone (PVP), and borohydride is preferably 1: (2-5): (1 to 10), more preferably 1: (2.5-4.5): (4 to 8), most preferably 1: (3-4): (5-6). In the present invention, the mass ratio of the water-soluble gold precursor to the magnetic nickel-cobalt oxide carrier is preferably not more than 0.1, more preferably (0.05 to 10): 100, most preferably (1-2): 100.
in the invention, the water-soluble gold precursor, the polyvinylpyrrolidone, the magnetic nickel-cobalt oxide carrier, the borohydride and the water are preferably mixed by stirring, and the stirring and mixing speed is not particularly limited, so that the raw materials can be uniformly mixed; in a specific embodiment of the present invention, the speed of the stirring and mixing is preferably 600rpm; the mixing sequence is preferably that a water-soluble gold precursor is dissolved in the first part of water to obtain a gold precursor solution; the gold precursor solution, polyvinylpyrrolidone and second part of water are mixed for the first time to obtain a mixed solution; secondly mixing the mixed solution and a magnetic nickel cobalt oxide carrier to obtain a mixed dispersion liquid; dissolving borohydride in the residual water to obtain a borohydride solution; and thirdly mixing the borohydride salt solution and the mixed dispersion liquid. In the invention, the concentration of the gold precursor solution is preferably 4-10 mg/mL, and more preferably 5-6 mg/mL; the concentration of the borohydride salt solution is preferably 1 to 2mg/mL, more preferably 1.5mg/mL. In the present invention, the time of the first mixing is preferably 60 to 120min, more preferably 80 to 100min; in the first mixing process, PVP adsorbs and disperses gold ions in the water-soluble gold precursor; the time for the second mixing is preferably 20 to 60min, more preferably 30 to 40min; the time for the third mixing is not particularly limited, and the raw materials can be uniformly mixed; the dropping speed is not specially limited, and the dropping can be carried out at a constant speed.
In the present invention, the temperature of the reduction reaction is preferably 25 to 50 ℃, more preferably 30 to 45 ℃, and most preferably 35 to 40 ℃; the time for the reduction reaction is preferably 1 to 4 hours, more preferably 2 to 3 hours, and most preferably 2.5 hours. In the invention, the surface functional groups of polyvinylpyrrolidone (PVP) are hydrophobic functional groups and hydrophilic functional groups, and the PVP has the functions of self-assembly and orientation guide, and has the functions of adsorbing, wrapping and dispersing gold ions in a solution and avoiding the aggregation of the gold ions in the solution.
After the reduction reaction, the invention preferably further comprises the steps of carrying out solid-liquid separation on the system of the reduction reaction, and sequentially washing and drying the obtained solid product with hot water to obtain the magnetic nickel cobalt oxide supported gold catalyst. The solid-liquid separation mode is not particularly limited, and the solid-liquid separation mode known to those skilled in the art can be adopted, such as filtration; the temperature of the hot water for hot water washing is preferably 80-100 ℃, and more preferably 90 ℃; the invention has no special limit on the times of hot water washing, and can remove PVP, water-soluble anions and cations on the surface of the catalyst completely. In the present invention, the drying temperature is preferably 80 to 110 ℃, more preferably 90 to 100 ℃; the drying time is preferably 12 to 14 hours, and more preferably 13 hours; the drying is preferably carried out in an oven.
The invention also provides the application of the magnetic nickel cobalt oxide supported gold catalyst in the technical scheme or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method in the technical scheme in the preparation of 2,5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural oxidation.
The invention also provides a preparation method of 2,5-furandicarboxylic acid, which comprises the following steps:
mixing 5-hydroxymethylfurfural, a magnetic nickel-cobalt oxide supported gold catalyst and water, and introducing oxygen to perform an oxidation reaction to obtain 2,5-furandicarboxylic acid;
the magnetic nickel cobalt oxide supported gold catalyst is the magnetic nickel cobalt oxide supported gold catalyst in the technical scheme or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method in the technical scheme.
In the invention, the preparation method of 2,5-furandicarboxylic acid is carried out according to the route shown in formula (1), and little 2,5-diformylfuran is generated in the preparation process, and finally, the target product 2,5-furandicarboxylic acid is generated by conversion, and no other side products are generated in the reaction process.
5-hydroxymethyl furfural → 5-hydroxymethyl-2-furancarboxylic acid → 5-formyl-2-furancarboxylic acid → 2,5-furandicarboxylic acid formula (1).
In the present invention, the ratio of the amount of the substance of 5-hydroxymethylfurfural to the mass of the magnetic nickel-cobalt oxide-supported gold catalyst is preferably 1mmol: (10-40) mg, more preferably 1mmol: (15-35) mg, most preferably 1mmol: (20-30) mg.
In the present invention, the ratio of the mass of 5-hydroxymethylfurfural to the volume of water is preferably 1mg: (0.06 to 0.1) mL, more preferably 1mg: (0.07 to 0.09) mL, most preferably 1mg:0.08mL.
Before the oxygen is introduced, the air in the reaction device is preferably removed, the air is preferably removed by introducing oxygen into the reaction device and purging the reaction device to remove the air, and the purging time is preferably 2-5 min, and more preferably 3-4 min. In the present invention, the temperature of the oxidation reaction is preferably 100 to 130 ℃, more preferably 105 to 125 ℃, and most preferably 110 to 120 ℃; the time of the oxidation reaction is preferably 0.5 to 8 hours, more preferably 2 to 6 hours, and most preferably 4 to 5 hours; the pressure of oxygen during the oxidation reaction is preferably 1 to 10bar, more preferably 2 to 8bar, and most preferably 5 to 6bar.
The apparatus to be used in the oxidation reaction of the present invention is not particularly limited, and a reaction apparatus known to those skilled in the art may be used. In the embodiment of the present invention, the oxidation reaction is preferably performed in a high pressure reaction vessel; the autoclave preferably has a polytetrafluoroethylene liner.
After the oxidation reaction, the invention preferably further comprises cooling the system of the oxidation reaction to room temperature to obtain 2,5-furandicarboxylic acid. In the invention, the cooling mode is preferably ice-water bath cooling; in the present invention, the cooling time is not particularly limited, and the cooling time may be as long as the cooling time is room temperature.
In the magnetic nickel cobalt oxide supported gold catalyst adopted by the invention, rich oxygen cavities and active oxygen species exist on the surface of a magnetic nickel cobalt oxide carrier, so that the conversion capability of the catalyst and the capability of benefiting molecular oxygen are greatly enhanced, small and uniform gold nanoparticles loaded on the surface of the magnetic nickel cobalt oxide carrier have very strong catalytic activity, 5-hydroxymethylfurfural substrate molecules are adsorbed and activated, and the 5-hydroxymethylfurfural is efficiently and specifically converted into 2,5-furandicarboxylic acid at lower temperature and oxygen pressure within shorter time under the synergistic effect of the magnetic nickel cobalt oxide carrier and the gold nanoparticles; in addition, the catalyst has excellent catalytic activity under the environment-friendly condition (water is used as a solvent, molecular oxygen is used as an oxidant), an inorganic acid-base additive or an organic oxidant is not required to be additionally used, the selectivity of the target product 2,5-furandicarboxylic acid is extremely high, the stability of the catalyst is good, the separation of the catalyst and the product can be realized through a simple physical magnetic separation mode, the cyclic utilization rate of the catalyst is high, the production cost of 2,5-furandicarboxylic acid is low, and the pollution to the environment is small.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 2.91g of Co (NO) 3 ) 2 ·6H 2 Adding O and 30mL of deionized water into a 50mL hydrothermal kettle lining, adding 2.91g of urea, magnetically stirring at 600rpm at normal temperature for 1.5h, and packagingPutting the hydrothermal kettle into a drying oven at 110 ℃ for hydrothermal reaction for 4h, naturally cooling to room temperature, filtering, putting the obtained light pink solid into the drying oven at 100 ℃ for drying for 13h, roasting for 4h at 400 ℃ in an air atmosphere, and reducing for 0.5h at 350 ℃ and under the hydrogen pressure of 0.1MPa to obtain magnetic zero-valent cobalt;
(2) Adding 0.1g of magnetic zero-valent cobalt into 100mL of deionized water, performing ultrasonic treatment for 10min, and adding 1.2g of Ni (NO) 3 ) 2 ·6H 2 O, stirring at 300rpm for 10min, adding Na 2 CO 3 The pH value is adjusted to 9, the precipitate is precipitated for 2 hours under the condition of stirring at room temperature, the filtration is carried out, the obtained solid product is washed by water and dried for 13 hours in an oven at 100 ℃, grinding for 1h, and calcining at 400 deg.C for 2h in air atmosphere to obtain magnetic Ni-Co oxide carrier (Co is known by XRD analysis 3 O 4 ) 1/3 (NiO) 3 Marked as CoNi 3 O y Y is 13/3);
(3) 0.4mL of HAuCl at a concentration of 5mg/mL 4 The solution (containing 2mg gold) and 4mg PVP with a molecular weight of 10000 were added to 200mL deionized water, stirred at 600rpm for 30min, and 400mg CoNi was added 3 O y Stirring for 30min, dissolving 10mg of sodium borohydride in 200mL of deionized water, dropwise adding the obtained sodium borohydride solution into the solution, carrying out reduction reaction for 2h at room temperature under the stirring condition, filtering, washing the obtained solid product with hot water, and drying in an oven at 100 ℃ for 13h to obtain the magnetic nickel-cobalt oxide supported gold catalyst (marked as 0.5% of Au/CoNi) 3 O y The loading of Au was 0.5 wt%).
The molar ratio of nickel to cobalt in the magnetic nickel cobalt oxide support as measured by ICP-MS was 3.
0.5% of Au/CoNi prepared in this example 3 O y The transmission electron microscope images of (a) are shown in fig. 1-2, and the inset in fig. 2 is the particle size statistical result shown in fig. 2, wherein the particle size statistical result is obtained statistically according to the TEM result in fig. 2. As can be seen from FIGS. 1 and 2, 0.5% of Au/CoNi 3 The Oy catalyst is one spherical nanometer particle with highly dispersed Au nanometer particle dispersed in CoNi 3 The surface of Oy; height ofResolving 0.21nm lattice fringes shown by an electron microscope image, and assigning the lattice fringes as a (111) crystal face of Au; the nano-particle size of Au is about 2-4 nm, and the average particle size is 2.2 +/-0.2 nm; the magnetic nickel cobalt oxide supported gold catalyst prepared by the invention belongs to a nano-scale catalyst.
The XRD patterns of the respective products during the preparation of the magnetic nickel cobalt oxide support in this example are shown in fig. 3. As can be seen from FIG. 3, urea and divalent cobalt ions are hydrothermally reacted for 4h at 110 ℃ to generate cobalt carbonate; roasting and decomposing the cobalt carbonate at 400 ℃ to generate cobaltosic oxide, and then reducing the cobaltosic oxide for 0.5h at 350 ℃ in a hydrogen atmosphere to obtain zero-valent cobalt; the zero-valent cobalt and the divalent nickel ions generate a mixture of nickel carbonate and cobalt under the action of sodium carbonate, and a cobalt-nickel composite oxide is generated during high-temperature roasting.
Example 2
A magnetic nickel cobalt oxide-supported gold catalyst was prepared by the method of example 1, except that Ni (NO) was used in step (2) 3 ) 2 ·6H 2 The mass of O was 0.4g, and a magnetic nickel-cobalt oxide carrier (the composition of the carrier was confirmed by XRD analysis to be (Co) 3 O 4 ) 1/3 (NiO) 1 Marked as CoNi 1 O y Y is 7/3); step (3) obtaining a magnetic nickel cobalt oxide supported gold catalyst (as 0.5% 1 O y The loading of Au was 0.5 wt%).
Example 3
A magnetic nickel cobalt oxide-supported gold catalyst was prepared by the method of example 1, except that Ni (NO) was used in step (2) 3 ) 2 ·6H 2 The mass of O was 2g, and a magnetic nickel-cobalt oxide carrier was obtained (the composition of the carrier was confirmed by XRD analysis to be (Co) 3 O 4 ) 1/3 (NiO) 5 Marked as CoNi 5 O y Y is 19/3); the magnetic nickel cobalt oxide supported gold catalyst obtained in step (3) (0.5% of Au/CoNi 5 O y The loading of Au was 0.5 wt%).
The XRD patterns of the magnetic nickel cobalt oxide carriers of different Co/Ni ratios prepared in examples 1 to 3 are shown in fig. 4,as can be seen from FIG. 4, the chemical compositions of the carriers prepared in examples 1 to 3 were (Co) 3 O 4 ) 1/3 (NiO) 3 (i.e., coNi) 3 O y )、(Co 3 O 4 ) 1/3 (NiO) 1 (i.e., coNi) 1 O y ) And (Co) 3 O 4 ) 1/3 (NiO) 5 (i.e., coNi) 5 O y )。
Example 4
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, differing from example 1 in that HAuCl was used in step (3) 4 The volume of the solution (containing 4mg of gold) was 0.8mL; the magnetic nickel cobalt oxide supported gold catalyst obtained in step (3) (as 1% of Au/CoNi) 3 O y The loading of Au was 1 wt%).
Example 5
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, differing from example 1 in that HAuCl was used in step (3) 4 The volume of the solution (containing 8mg of gold) was 1.6mL; the magnetic nickel cobalt oxide supported gold catalyst obtained in step (3) (noted as 2% Au/CoNi) 3 O y The loading of Au was 2 wt%).
Example 6
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, except that the calcination temperature in step (2) was 300 ℃.
Example 7
A magnetic nickel cobalt oxide-supported gold catalyst was prepared according to the method of example 1, except that the calcination temperature in step (2) was 500 ℃.
Example 8
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, except that the calcination temperature in step 2 was 600 ℃.
Comparative example 1
A catalyst was prepared as in example 1, except that Ni (NO) was not added in step (2) of example 2 3 ) 2 ·6H 2 O to obtain a magnetic cobalt oxide carrier CoO x (CoO-Co 3 O 4 Wherein CoO and Co 3 O 4 In a molar ratio of 1);
a catalyst was prepared by following step (3) of example 1, differing from step (3) of example 1 in that CoO x Substitute CoNiO y To obtain a catalyst (noted as 0.5% Au/CoO-Co) 3 O 4 The supported amount of Au was 0.5 wt%).
Comparative example 2
2.91g of Co (NO) 3 ) 2 ·6H 2 Dissolving O in 100mL of deionized water, adding sodium carbonate until the pH value is 9, precipitating for 2h at room temperature under the stirring condition, filtering, washing the obtained solid product with water, drying for 13h in an oven at 100 ℃, grinding for 1h, and roasting for 2h at 400 ℃ in an air atmosphere to obtain a carrier NiO;
a catalyst was prepared by following step (3) of example 1, differing from step (3) of example 1 in that NiO was substituted for CoNiO y The catalyst was obtained (as 0.5% by weight Au/NiO, with the amount of Au supported being 0.5% by weight).
Comparative example 3
2.91g of Ni (NO) 3 ) 2 ·6H 2 O and 2.91g Co (NO) 3 ) 2 ·6H 2 Adding O into 100mL of deionized water, adding sodium carbonate to adjust the pH value to 9, carrying out coprecipitation for 2h at room temperature and 600rpm, filtering, washing the obtained solid product with water, drying in an oven at 100 ℃ for 13h, grinding for 1h, and roasting at 400 ℃ for 4h in an air atmosphere to obtain a carrier (CoNi) 3 O-cp)；
A catalyst was prepared by following step (3) of example 1, differing from step (3) of example 1 in that CoNi 3 O-cp instead of CoNiO y To obtain a catalyst (0.5% of Au/CoNi 3 O-cp, au loading 0.5 wt%).
Comparative example 4
Example 1 CoNi obtained in step (2) 3 O y 。
Comparative example 5
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, except that the calcination temperature in step (2) was 200 ℃.
Comparative example 6
A magnetic nickel cobalt oxide supported gold catalyst was prepared according to the method of example 1, except that the calcination temperature in step (2) was 700 ℃.
Application example 1
Placing the carriers prepared in comparative examples 1 to 4, the catalysts prepared in examples 1 to 8 and the catalysts prepared in comparative examples 1 to 3 in inner containers of a reaction kettle, adding 5mL of deionized water, 5mmol of 5-Hydroxymethylfurfural (HMF) and stirring magnetons, purging the gas in the kettle for 3min by using oxygen to empty the air in the kettle, filling 10bar of oxygen into the autoclave, placing the reaction kettle in a constant-temperature oil bath at 120 ℃ and 600rpm after an air tightness test, reacting for 8h, cooling the autoclave to room temperature by using an ice-water mixture, taking a supernatant of a reaction solution by using a disposable syringe, filtering by using a 0.45nm filter head, taking 1mL of filtrate to dilute the filtrate by 25 times, placing the filtrate into a 2mL sample feeding bottle, and carrying out quantitative analysis on catalytic results by using an Agilent liquid chromatograph, wherein the catalytic results of the catalysts prepared in examples 1 to 5, the carriers prepared in comparative examples 1 to 3, the catalysts prepared in comparative examples 1 to 8, and the carriers prepared in comparative examples 1 to 8 are shown in Table 1, and the catalytic results of the catalysts prepared in the comparative examples 1 to 8 are shown in the same mass as the carriers prepared in Table 1 to 8; the amount of substance of Au in the catalysts prepared in examples 1 to 8 and the catalysts prepared in comparative examples 1 to 3 was 0.05mmol (i.e., HMF/Au molar ratio = 100).
The addition amount of the support prepared in comparative examples 1 to 4 was 200mg, and the amount of substance of Au in the catalysts prepared in examples 1 to 8 and the catalysts prepared in comparative examples 1 to 3 was 0.05mmol (i.e., HMF/Au molar ratio = 100).
TABLE 1 catalysis results of the supports prepared in comparative examples 1 to 4, the catalysts prepared in examples 1 to 5, and the catalysts prepared in comparative examples 1 to 3
Figure GDA0003842304280000161
As can be seen from Table 1, pure NiO supportBody and CoO x The support showed weak activity for the oxidative conversion of 5-hydroxymethylfurfural with a yield of 2,5-furandicarboxylic acid of 0%. CoNi prepared by step method 3 O y The carrier shows weak activity for oxidizing 5-hydroxymethylfurfural to prepare 2,5-furandicarboxylic acid, the conversion rate of 5-hydroxymethylfurfural reaches 18%, and the yield of 2,5-furandicarboxylic acid is 0%. CoNi prepared by coprecipitation method 3 O x -cp Carrier vs. CoNi prepared by fractional step method 3 O y For the carrier, the catalytic activity is reduced, the conversion rate of 5-hydroxymethylfurfural is only 9%, and 2,5-furandicarboxylic acid is not generated. After supporting gold, the catalyst exhibits excellent catalytic activity. 0.5% of Au/CoNi 3 O y The conversion rate of catalytic oxidation of 5-hydroxymethylfurfural reaches 100%, and the yield of 2,5-furandicarboxylic acid also reaches 100%; au/CoNi 3 O x The conversion rate of the-cp catalyst for catalytic oxidation of 5-hydroxymethylfurfural reaches 83%, and the yield of 2,5-furandicarboxylic acid is 22%. From this, it was found that gold is an active substance for producing 2,5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, and 0.5% of Au/CoNi 3 O y The catalytic activity of the catalyst is better than 0.5% 3 O x -a cp catalyst. Illustrating the step-wise preparation of CoNi 3 O y The carrier is more beneficial to preparing 2,5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, and the magnetism of the catalyst is kept.
0.5% of Au/CoO x On the catalyst, the conversion of 5-hydroxymethylfurfural was 52.4% and the yield of 2,5-furandicarboxylic acid was 9.5%, indicating that the catalyst has a higher oxidative conversion activity for 5-hydroxymethylfurfural but a lower rate of 2,5-furandicarboxylic acid formation. On a 0.5% Au/NiO catalyst, the conversion of 5-hydroxymethylfurfural was 86.8%, the yield of 2,5-furandicarboxylic acid was 46.1%, and the catalytic activity of the catalyst gradually increased with the addition of the Co component; 0.5% of Au/CoNi 3 O y The catalyst exhibits optimum catalytic activity. This suggests that the interaction of the elements in the catalyst is critical to the catalytic activity of the gold-based catalyst.
With the increasing loading of gold, the catalytic activity of the catalystDecreasing gradually, 0.5% of Au/CoNi 3 O y The catalyst shows the optimal catalytic activity, and when the loading capacity of gold is lower, small and uniform gold nanoparticles can be obtained and are highly dispersed on the carrier; generally, gold nanoparticles with small particle size have better catalytic performance.
TABLE 2 catalysis results of the catalysts prepared in examples 1, 6 to 8
Figure GDA0003842304280000171
Figure GDA0003842304280000181
As can be seen from Table 2, the optimum calcination temperature of the support was 400 ℃, and as the temperature increased, the conversion of 5-hydroxymethylfurfural by the catalyst gradually decreased, and the yield of 2,5-furandicarboxylic acid also gradually decreased. The roasting temperature of 300 ℃ can cause that the nickel carbonate can not be completely decomposed and pure cobalt-nickel composite oxide can not be obtained, thereby causing the reduction of the catalytic activity of the catalyst; the catalytic performance of the catalyst taking the magnetic nickel-cobalt oxide carrier obtained by roasting at 600 ℃ as a carrier is poor, and the nano structure and the morphology of the catalyst carrier are possibly damaged due to high-temperature roasting.
The magnetic test results of the reaction solution after the magnetic nickel-cobalt oxide supported gold catalyst prepared in example 1 catalyzes 5-hydroxymethylfurfural to oxidize 2,5-furandicarboxylic acid are shown in fig. 5. As can be seen from fig. 5, the magnetic nickel cobalt oxide supported gold catalyst prepared in example 1 can be firmly adsorbed on the sidewall of the sample bottle by the magnet, which shows that the catalyst prepared in the present invention has very strong magnetism, and the recovery of the magnetic nickel cobalt oxide supported gold catalyst can be realized by a magnetic separation method.
The recovered magnetic nickel cobalt oxide supported gold catalyst was washed and dried, and then used again for catalytic reaction according to the method of application example 1, and the catalytic result is shown in fig. 6. As can be seen from fig. 6, after the magnetic nickel-cobalt oxide supported gold catalyst prepared by the present invention is recycled for 5 times, the conversion rate of 5-Hydroxymethylfurfural (HMF) is still 100%, and the selectivity of 2,5-furandicarboxylic acid (FDCA) is still 100%, which indicates that the magnetic nickel-cobalt oxide supported gold catalyst provided by the present invention has high recycling rate and good stability.
Application examples 2 to 8
2,5-furandicarboxylic acid was prepared according to the method of application example 1, using the magnetic nickel-cobalt oxide supported gold catalyst prepared in example 1 as a catalyst, the preparation conditions of application examples 2 to 8, the conversion of 5-hydroxymethylfurfural, and the selectivity of each component in the reaction solution, and the results are shown in table 3.
Comparative examples 7 to 9
2,5-furandicarboxylic acid was prepared according to the method of application example 1, using the magnetic nickel-cobalt oxide supported gold catalyst prepared in example 1 as a catalyst, the preparation conditions of comparative examples 7 to 9, the conversion of 5-hydroxymethylfurfural and the selectivity of each component in the reaction liquid were applied, and the results are shown in table 3.
TABLE 3 preparation conditions of comparative examples 7 to 9, conversion of 5-hydroxymethylfurfural and selectivity of each component in the reaction solution
Figure GDA0003842304280000191
The catalytic results of application example 1 in table 3 are catalyst results using the magnetic nickel cobalt oxide supported gold catalyst prepared in example 1 as a catalyst. As can be seen from table 3, in the preparation of 2,5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural with the magnetic nickel-cobalt oxide supported gold catalyst prepared in the example of the present invention, (1) as the oxygen pressure is decreased from 10bar by 1bar, the conversion of 5-hydroxymethylfurfural is decreased from 100% to 86%, and the selectivity of 2,5-diformylfuran, 5-hydroxymethyl-2-furancarboxylic acid and 5-formyl-2-furancarboxylic acid is respectively increased from 0 to 3%, 9% and 24%; the yield of 2,5-furandicarboxylic acid was reduced from 100% to 57%; note that the oxygen pressure was 0.5% of Au/CoNi 3 O y The product distribution and the generation of target products of the 5-hydroxymethylfurfural catalytic oxidation by the catalyst have larger influence, and the oxygen pressureThe force is 10bar, 5-hydroxymethylfurfural can be completely and catalytically converted to prepare 2,5-furandicarboxylic acid, and the excessive oxygen pressure has no great promotion effect on the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2,5-furandicarboxylic acid. (2) As the molar ratio of HMF/Au increases from 100 to 400,5-hydroxymethylfurfural conversion decreases from 100% to 72%, the selectivity of 2,5-diformylfuran, 5-hydroxymethyl-2-furancarboxylic acid and 5-formyl-2-furancarboxylic acid rises from 0 to 4%, 13% and 33%, respectively; the yield of 2,5-furandicarboxylic acid was reduced from 100% to 36%; shows the molar ratio of HMF/Au, i.e. the amount of catalyst used for 0.5Au/CoNi 3 O y The product distribution of the catalytic oxidation of 5-hydroxymethylfurfural by the catalyst and the generation of a target product have great influence, and 5-hydroxymethylfurfural can be completely catalytically converted to prepare 2,5-furandicarboxylic acid when the HMF/Au molar ratio is = 100. (3) In the initial stage (within 1 h) of the oxidation reaction, the conversion rate of 5-hydroxymethylfurfural reaches 57%, and the selectivity of 2,5-diformylfuran, 5-hydroxymethyl-2-furancarboxylic acid, 5-formyl-2-furancarboxylic acid and 2,5-furandicarboxylic acid is 5%, 29%, 36% and 30% respectively; with the extension of the reaction time, the selectivity of 2,5-diformylfuran, 5-hydroxymethyl-2-furancarboxylic acid and 5-formyl-2-furancarboxylic acid is gradually reduced, and finally the selectivity is 0 after the reaction is carried out for 8 hours; the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2,5-furandicarboxylic acid are increased along with the extension of the reaction time and reach 100 percent after the reaction is carried out for 8 hours, and the overlong oxidation time has no great promotion effect on the conversion rate of 5-hydroxymethylfurfural and the selectivity of 2,5-furandicarboxylic acid; note that in 0.5Au/CoNi 3 O y On the catalyst, the oxidation of HMF to produce 2,5-furandicarboxylic acid is a slow, continuous process that requires sufficient reaction time to complete the conversion.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. The magnetic nickel cobalt oxide supported gold catalyst is characterized by comprising a magnetic nickel cobalt oxide carrier and gold nanoparticles supported on the magnetic nickel cobalt oxide carrier;
the chemical composition of the magnetic nickel-cobalt oxide carrier is CoNi x O y Wherein x is 1-5,y which satisfies CoNi x O y The number of oxygen atoms in the valence state zero; the loading capacity of the gold nanoparticles is less than or equal to 10wt%;
the preparation method of the magnetic nickel cobalt oxide supported gold catalyst comprises the following steps:
mixing a water-soluble cobalt precursor, a precipitator and water, and then sequentially carrying out hydrothermal reaction, first roasting and hydrogen reduction reaction to obtain magnetic zero-valent cobalt;
mixing the magnetic zero-valent cobalt, a water-soluble nickel precursor, water-soluble carbonate and water, and sequentially performing precipitation and second roasting to obtain a magnetic nickel-cobalt oxide carrier;
and mixing a water-soluble gold precursor, polyvinylpyrrolidone, the magnetic nickel-cobalt oxide carrier, borohydride and water, and carrying out reduction reaction to obtain the magnetic nickel-cobalt oxide supported gold catalyst.
2. The magnetic nickel cobalt oxide supported gold catalyst of claim 1 wherein the gold nanoparticles have an average particle size of 2.2 ± 0.2nm;
the average particle size of the magnetic nickel cobalt oxide supported gold catalyst is 20 +/-5 nm.
3. The method for preparing a magnetic nickel cobalt oxide supported gold catalyst according to any one of claims 1 to 2, comprising the steps of:
mixing a water-soluble cobalt precursor, a precipitator and water, and then sequentially carrying out hydrothermal reaction, first roasting and hydrogen reduction reaction to obtain magnetic zero-valent cobalt;
mixing the magnetic zero-valent cobalt, a water-soluble nickel precursor, water-soluble carbonate and water, and sequentially performing precipitation and second roasting to obtain a magnetic nickel-cobalt oxide carrier;
and mixing a water-soluble gold precursor, polyvinylpyrrolidone, the magnetic nickel-cobalt oxide carrier, borohydride and water, and carrying out reduction reaction to obtain the magnetic nickel-cobalt oxide supported gold catalyst.
4. The method according to claim 3, wherein the molar ratio of the water-soluble cobalt precursor to the precipitant is 1: (1-2).
5. The preparation method according to claim 3 or 4, characterized in that the temperature of the hydrothermal reaction is 90-180 ℃ and the time is 2-8 h;
the temperature of the first roasting is 300-600 ℃, and the time is 3-5 h;
the temperature of the hydrogen reduction reaction is 250-450 ℃, and the time is 0.5-2 h.
6. The preparation method according to claim 3, wherein the molar ratio of the magnetic zero-valent cobalt to the water-soluble nickel precursor to the water-soluble carbonate is 1: (1-5): (0.5 to 2.5);
the temperature of the second roasting is that the temperature of the precipitation is 300-600 ℃, and the time is 2-5 h.
7. The preparation method according to claim 3, wherein the mass ratio of the water-soluble gold precursor to the polyvinylpyrrolidone to the borohydride salt is 1: (2-5): (1-10);
the mass ratio of the water-soluble gold precursor to the magnetic cobalt-nickel composite oxide is less than or equal to 0.1;
the temperature of the reduction reaction is 25-50 ℃ and the time is 1-4 h.
8. Use of the magnetic nickel cobalt oxide supported gold catalyst according to any one of claims 1 to 2 or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method according to any one of claims 3 to 7 in the preparation of 2,5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural oxidation.
9. A preparation method of 2,5-furandicarboxylic acid is characterized by comprising the following steps:
mixing 5-hydroxymethylfurfural, a magnetic nickel-cobalt oxide supported gold catalyst and water, and introducing oxygen to perform an oxidation reaction to obtain 2,5-furandicarboxylic acid;
the magnetic nickel cobalt oxide supported gold catalyst is the magnetic nickel cobalt oxide supported gold catalyst according to any one of claims 1 to 2 or the magnetic nickel cobalt oxide supported gold catalyst prepared by the preparation method according to any one of claims 3 to 7.
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