CN114789047A - Preparation method and application of surface boron-doped nickel oxide catalyst - Google Patents

Preparation method and application of surface boron-doped nickel oxide catalyst Download PDF

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CN114789047A
CN114789047A CN202210333034.7A CN202210333034A CN114789047A CN 114789047 A CN114789047 A CN 114789047A CN 202210333034 A CN202210333034 A CN 202210333034A CN 114789047 A CN114789047 A CN 114789047A
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boron
nickel
nickel oxide
oxide catalyst
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李广社
马明伟
李莉萍
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Jilin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C07D307/44—Furfuryl alcohol
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Abstract

The invention is suitable for the technical field of material synthesis and organic synthesis, and provides a preparation method of a surface boron-doped nickel oxide catalyst, wherein the surface boron-doped nickel oxide catalyst is synthesized by raw materials of soluble nickel salt, soluble boric acid or borate and citric acid, and the cost is controllable; the preparation method adopts a sol-gel method, obtains the surface boron-doped nickel oxide nanoparticles with different particle sizes by regulating the nickel/boron ratio and the calcination temperature, is simple, easy to operate and good in stability, has high specific surface area and rich acid-base sites, is applied to Meerwein-Ponndorf-Verley reaction of furfural, shows good catalytic activity, circulation stability and reproducibility under the conditions of low temperature and normal pressure, and has good industrial application prospect.

Description

Preparation method and application of surface boron-doped nickel oxide catalyst
Technical Field
The invention relates to the technical field of material synthesis and organic synthesis, in particular to a preparation method and application of a surface boron-doped nickel oxide catalyst.
Background
Due to the limited natural resources of the earth and the increased energy demand of mankind, the conversion of biomass into fuels and chemicals is of great significance in the rapidly developing human society. The biomass energy is a novel energy which is wide in distribution, large in total amount, renewable and environment-friendly, has the greatest compatibility with modern industrial technology and modern life, and has the greatest substitution potential for fossil energy.
Furfuryl alcohol, the chemical name of which is 2-hydroxymethyl furan, is an important biomass-derived organic raw material and is widely applied to the industries of synthetic fibers, rubber, resin, spices, medicines, pesticide intermediates and the like, the largest consumption is for manufacturing the synthetic fibers and furan resin, and the proportion of the furfuryl alcohol resin in China is 80-90%, wherein the furfuryl alcohol resin can be used for preparing a plasticizer with excellent cold resistance. The furfuryl alcohol is a product subjected to selective hydrogenation of biomass derivative furfural, wherein Meerwein-Ponndorf-Verley (MPV) reduction reaction is a very important hydrogenation method in the reaction process, and the whole reaction process is relatively safe and green and is compounded with a green sustainable development concept compared with hydrogenation reaction using hydrogen or formic acid as a hydrogen source due to the fact that isopropanol is used as a solvent and a hydrogen source. At present, a plurality of catalytic materials for MPV reaction of furfural are mainly constructed by an acid-base synergistic catalysis mechanism, and mainly comprise metal organic hybrid materials, molecular sieves, metal oxides and other catalysts, wherein the materials have abundant acid-base sites and are very critical for improving the catalytic reaction performance. However, these materials have certain drawbacks, such as: non-regenerability (incapable of high-temperature calcination) of metal organic hybrid materials and difficulty in controlling catalytic selectivity of molecular sieves (abundance)
Figure BDA0003573693620000011
Acid promotes the generation of byproducts), low catalytic activity of metal oxides (relatively low specific surface area causes few catalytic active sites), inability of large-scale synthesis of materials (synthesis process has no economic advantage), and the like. In recent years, for metal oxide catalysts, researchers mainly adopt the following construction strategies to improve the performance of the catalyst of the metal oxide in the MPV reaction of furfural: (1) modulating the chemical state of the metal active site by multi-metal compounding; (2) reducing the particle size of the catalyst to nanoscale, achieving more active sitesExposing; (3) the composite material is compounded with non-metal materials such as carbon, nitrogen, phosphorus and the like to improve the specific surface area and realize the construction of new active sites and the like. However, the existing strategies to improve the catalytic performance of metal oxides in the furfural MPV reaction are still very limited, and the realization of the nano-size of the particles and the doping method of metals or nonmetals does not improve the catalytic activity qualitatively.
Therefore, the invention provides an effective surface boron-doped nickel oxide catalyst, and the particle size is controlled and the acid-base concentration is improved through the nickel/boron ratio so as to effectively improve the catalytic activity, so that the MPV reaction of the furfural can be efficiently carried out under the conditions of normal pressure and below 100 ℃. For boron doping of nickel oxide or other metal oxides, previous reports mostly focus on bulk phase doping research, and no report is provided at home and abroad about boron surface doped nickel oxide materials.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method and application of a surface boron-doped nickel oxide catalyst, and aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a surface boron-doped nickel oxide catalyst comprises the following steps:
step S1: adding nickel salt, boric acid or borate, citric acid and deionized water into a beaker, and stirring for a period of time at a certain temperature to obtain a solution;
step S2: placing the beaker obtained in the step S1 in an oven at a certain temperature for drying for a certain time to obtain xerogel;
step S3: the sample obtained in step S2 was calcined in a muffle furnace, and then the sample was washed with hot water, suction filtered, and dried.
Further, the molar ratio of nickel/boron of the surface boron-doped nickel oxide is 3:0-3:2, the nickel salt is selected from one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, the boric acid or borate is selected from one of boric acid, sodium tetraborate and potassium tetraborate, the citric acid is 6-24mmol, and the deionized water is 10-50 ml.
Further, in the step S1, the dissolution temperature for the dissolution of nickel salt, boric acid or borate, and citric acid is 60-100 ℃, and the time is 5-60 min.
Further, in the step S2, the drying temperature range of the xerogel obtained is 100-150 ℃, and the time is 2-20 h.
Further, in the step S3, the calcination temperature is controlled to be 350-.
Further, in the step S3, for the washing of the calcined sample, the hot water temperature is in the range of 40 to 100 ℃.
The catalyst used as a hydrogenation catalyst prepared by the preparation method of the surface boron-doped nickel oxide catalyst is applied to Meerwein-Ponndorf-Verley reaction of furfural.
Furthermore, in the Meerwein-Ponndorf-Verley reaction of the furfural, the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely the furfural, isopropanol and the catalyst, are mixed according to the proportion of 0.67mmol to 20mL to 0.1 g.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the prior reported nickel oxide or boron doping of other metal oxides, the surface boron-doped nickel oxide catalyst synthesized by the sol-gel method is concentrated on bulk phase doping, and the obtained surface boron-doped nickel oxide has the characteristics of effectively reducing the surface energy, preventing particles from being enlarged and further improving the specific surface area, and simultaneously introducing new acidic sites and improving the concentration of acid-base sites to the catalyst by the surface doping of boron.
2. Compared with the existing metal oxide catalyst, the surface boron-doped nickel oxide catalyst provided by the invention is applied to MPV (Meerwein-Ponndorf-Verley) reaction of furfural, has qualitative leap in catalytic performance, can be used for high-efficiency catalysis at normal pressure and low temperature (less than 100 ℃), has excellent cycle stability and reproducibility, and has good industrial application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the products prepared for all nickel/boron ratios of the examples.
FIG. 2 is a TEM image of the samples of examples 1, 2 and 3.
Fig. 3 is a graph of the catalytic performance of the furfural MPV reaction for the samples in examples 1, 2, 3.
Figure 4 is a graph of the cycling stability of the furfural MPV reaction for the samples in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Example 1
Preparation of sample #1 surface boron-doped Nickel oxide catalyst with Nickel/boron molar ratio of 3:0
Dissolving 12mmol of nickel nitrate and 12mmol of citric acid in 30ml of deionized water, stirring in a water bath at 90 ℃ for a period of time, placing in an oven at 120 ℃ for drying for 10h to obtain xerogel, uniformly grinding the xerogel, and calcining in a muffle furnace at 400 ℃ for 1h at the room temperature rate of 10 ℃/min. And then washing with hot water at 90 ℃, carrying out suction filtration and drying to obtain a final sample. The catalytic reaction conditions are as follows: the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely furfural, isopropanol and the catalyst, are mixed according to the proportion of 0.67mmol to 20mL to 0.1 g. The XRD pattern of the flaky nickel-magnesium solid solution prepared in the example is shown in figure 1.
Example 2
Preparation of sample #2 surface boron-doped Nickel oxide catalyst with Nickel/boron molar ratio of 12:1
Dissolving 12mmol of nickel nitrate, 1mmol of boric acid and 12mmol of citric acid in 30ml of deionized water, stirring in a water bath at 90 ℃ for a period of time, placing in an oven at 120 ℃ for drying for 10h to obtain xerogel, uniformly grinding the xerogel, and calcining in a muffle furnace at 400 ℃ for 1h at the room temperature rate of 10 ℃/min. Then washing with hot water of 90 ℃, filtering and drying to obtain the final sample. The catalytic reaction conditions are as follows: the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely furfural, isopropanol and the catalyst are mixed according to the proportion of 0.67mmol, 20mL and 0.1 g. The XRD pattern of the flaky nickel-magnesium solid solution prepared in this example is shown in FIG. 1.
Example 3
Preparation of sample #3 surface boron-doped Nickel oxide catalyst with Nickel/boron molar ratio of 3:1
Dissolving 12mmol of nickel nitrate, 4mmol of boric acid and 12mmol of citric acid in 30ml of deionized water, stirring in a water bath at 90 ℃ for a period of time, placing in an oven at 120 ℃ for drying for 10h to obtain xerogel, uniformly grinding the xerogel, and calcining in a muffle furnace at 400 ℃ for 1h at the room temperature rate of 10 ℃/min. Then washing with hot water of 90 ℃, filtering and drying to obtain the final sample. The catalytic reaction conditions are as follows: the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely furfural, isopropanol and the catalyst are mixed according to the proportion of 0.67mmol, 20mL and 0.1 g. The XRD pattern of the flaky nickel-magnesium solid solution prepared in this example is shown in FIG. 1.
Example 4
Preparation of sample #4 surface boron-doped Nickel oxide catalyst with a Nickel/boron molar ratio of 3:2
Dissolving 12mmol of nickel nitrate, 8mmol of boric acid and 12mmol of citric acid in 30ml of deionized water, stirring in a water bath at 90 ℃ for a period of time, placing in an oven at 120 ℃ for drying for 10h to obtain xerogel, uniformly grinding the xerogel, and calcining in a muffle furnace at 400 ℃ for 1h at the room temperature rate of 10 ℃/min. And then washing with hot water at 90 ℃, carrying out suction filtration and drying to obtain a final sample. The catalytic reaction conditions are as follows: the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely furfural, isopropanol and the catalyst, are mixed according to the proportion of 0.67mmol to 20mL to 0.1 g.
Example 5
Characterization of sample structure, morphology and physicochemical properties
Through XRD characterization and physical and chemical property analysis of samples #1 to #4, as shown in FIG. 1 and Table 1, the results show that the samples with the nickel/boron molar ratios of 3:0, 12:1 and 3:1 are all cubic nickel oxide, the XRD peak positions of the nickel oxide are not shifted along with the doping of boron, and the boron doping positions are mainly on the surface by combining the difference of the nickel/boron molar ratios of the bulk phase and the surface. Meanwhile, the particle size is obviously reduced along with the surface doping of boron, which can be obtained through TEM (figure 2) and XRD analysis, so that the specific surface area of a sample can be increased by boron doping (obtained from N2-BET). In summary, the sample has a higher concentration of acid sites due to the surface doping of boron and small nanoparticles, but too high amount of boron doping makes the nickel oxide amorphous and therefore has a very low specific surface area and acid-base sites.
TABLE 1
Figure BDA0003573693620000061
Example 6
MPV reaction of furfural
The catalyst is filled into a 50ml round bottom flask with magnetons, furfural and isopropanol are added, a spherical condensing device is installed, performance test is carried out under an oil bath at a target temperature, and then the filtrate is detected by a gas phase mass spectrometer (GC-MS) to evaluate the catalytic performance. The catalytic reaction conditions are as follows: the temperature range of the catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the components of the reaction liquid, namely furfural, isopropanol and the catalyst, are mixed according to the proportion of 0.67mmol to 20mL to 0.1 g.
MPV reaction of furfural is carried out on samples #1 to #3 according to the test conditions, and a performance diagram is shown in figure 3, which shows that the surface boron-doped NiO has excellent catalytic performance under the conditions of normal pressure and low temperature. Meanwhile, a sample #3 is subjected to a cycle stability test, as shown in fig. 4 (conditions of 80 ℃, 2h and normal pressure), the catalyst has good catalytic performance after 19 cycles, and the sample after 19 cycles is calcined and regenerated at 400 ℃ for 20 cycles to remove surface humic acid, so that the catalytic performance is obviously improved, and the surface boron-doped NiO catalyst has good cycle stability and regenerability.
The working principle of the invention is as follows:
the catalyst is synthesized by soluble nickel salt, soluble boric acid or borate and citric acid raw materials, and the cost is controllable; the preparation method is a sol-gel method, and surface boron-doped nickel oxide nanoparticles with different particle sizes are obtained by regulating the nickel/boron ratio and the calcination temperature.
The above is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several variations and modifications without departing from the concept of the present invention, and these should be considered as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the practicability of the patent.

Claims (8)

1. A preparation method of a surface boron-doped nickel oxide catalyst is characterized by comprising the following steps:
step S1: adding nickel salt, boric acid or borate, citric acid and deionized water into a beaker, and stirring for a period of time at a certain temperature to obtain a solution;
step S2: putting the beaker obtained in the step S1 into an oven at a certain temperature for drying for a certain time to obtain xerogel;
step S3: the sample obtained in step S2 was calcined in a muffle furnace, and then the sample was washed with hot water, suction-filtered, and dried.
2. The method for preparing the surface boron-doped nickel oxide catalyst according to claim 1, wherein the molar ratio of nickel/boron of the surface boron-doped nickel oxide is 3:0-3:2, the nickel salt is selected from one of nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, the boric acid or the borate is selected from one of boric acid, sodium tetraborate and potassium tetraborate, the citric acid is 6-24mmol, and the deionized water is 10-50 ml.
3. The method of claim 2, wherein in step S1, the dissolution temperature of the nickel salt, boric acid or borate, and citric acid is 60-100 ℃ for 5-60 min.
4. The method as claimed in claim 1, wherein the drying temperature of the xerogel obtained in step S2 is 100-150 ℃ and the time is 2-20 h.
5. The method as claimed in claim 1, wherein in step S3, the calcination temperature is controlled to 350-800 ℃, the calcination time is 0.5-5h, and the temperature rise rate is 1-10 ℃/min.
6. The method of claim 5, wherein the hot water temperature ranges from 40 ℃ to 100 ℃ for the washing of the calcined sample in step S3.
7. A Meerwein-Ponndorf-Verley reaction applied to furfural as a catalyst for hydrogenation prepared by the method for preparing a surface boron-doped nickel oxide catalyst according to any one of claims 1 to 6.
8. The application of the surface boron-doped nickel oxide catalyst according to claim 7, wherein in the Meerwein-Ponndorf-Verley reaction of furfural, the temperature range of catalytic reaction is 50-100 ℃, the pressure is normal pressure, and the reaction liquid components of furfural, isopropanol and catalyst are mixed according to the proportion of 0.67mmol:20mL:0.1 g.
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