A Pt-PtOx@Mg(OH)2-F catalyst and a preparation method and application thereof

Abstract

This invention belongs to the field of biomass conversion technology, specifically relating to a Pt-PtO... x @Mg(OH)₂-F catalyst, its preparation method, and applications. The preparation method includes: sealing an open container containing magnesium chloride solution in a container containing ammonium carbonate and concentrated ammonia solution; heating the reaction and then filtering the solution in the open container to obtain a precipitate; calcining the precipitate to obtain magnesium oxide; adding chloroplatinic acid and polyvinylpyrrolidone to deionized water and stirring, then adding sodium borohydride and stirring, followed by adding magnesium oxide and stirring; filtering and collecting the precipitate; and thermally decomposing the precipitate to obtain Pt-PtO. x @Mg(OH)₂-F catalyst. This invention prepares the precursor magnesium oxide via a gas-liquid interface reaction, then loads platinum sites using a sol-gel method, and finally obtains flower-like spherical Pt-PtO through thermal decomposition in air. x The Mg(OH)2-F catalyst enabled the efficient conversion of furfural, a biomass platform compound, into furfuryl alcohol.

Description

Technical Field

[0001] This invention belongs to the field of biomass conversion technology, specifically relating to a Pt-PtO... x @Mg(OH)2-F catalyst, its preparation method and application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] With the depletion of fossil resources and the worsening of environmental problems, biomass resources have attracted great attention. Lignocellulose is one of the most abundant biomass compounds and has received high attention. Furfural, derived from lignocellulose biomass, is an important platform chemical with great potential as a renewable feedstock for the production of various value-added chemicals and biofuels. The selective hydrogenation of furfural to furfuryl alcohol is a key shift. Furfural has many applications, including fine chemicals, biofuel additives, furan resins, solvents, and pharmaceuticals. Furfuryl alcohol is a precursor to many industrially significant compounds such as furan resins, solvents, and pharmaceuticals, making its production a research hotspot in the fields of green chemistry and sustainable technology. The catalytic hydrogenation of furfural to furfuryl alcohol typically involves the use of heterogeneous catalysts due to their efficiency, selectivity, and ease of separation.

[0004] Currently, there are many types of catalysts for the preparation of furfural from furfural, such as industrial CuCr-based catalysts, biocatalysts (enzymes), and Pt / Pd-based catalysts. However, these catalysts still have many drawbacks in practical applications. First, Cr-based catalysts have potential toxicity or environmental pollution risks, limiting their widespread industrial application. Furthermore, their activity and selectivity are generally low, making it difficult to achieve efficient conversion. Second, biocatalysts are prone to deactivation under reaction conditions and have short lifespans, further increasing production costs and complexity. In addition, Pt / Pd catalysts rely on large amounts of precious metals, resulting in high costs, and the lack of in-depth analysis of the reaction mechanism makes optimization and improvement difficult. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a Pt-PtO x @Mg(OH)₂-F catalyst, its preparation method, and its application. This invention prepares magnesium oxide precursor via gas-liquid interface reaction, then loads platinum sites using a sol-gel method, and finally obtains flower-like spherical Pt-PtO through thermal decomposition in air. x The Mg(OH)2-F catalyst enabled the efficient conversion of furfural, a biomass platform compound, into furfuryl alcohol.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] Firstly, a Pt-PtO x The preparation method of @Mg(OH)2-F catalyst includes the following steps:

[0008] S1. Seal an open container containing magnesium chloride solution into a container containing ammonium carbonate and concentrated ammonia solution, heat the reaction, filter the solution in the open container to obtain a precipitate, and calcine the precipitate to obtain magnesium oxide.

[0009] S2. Chloroplatinic acid and polyvinylpyrrolidone were added to deionized water and stirred. Then sodium borohydride was added and stirred, followed by magnesium oxide and stirred. The precipitate was collected by filtration and thermally decomposed to obtain Pt-PtO. x @Mg(OH)2-F catalyst.

[0010] Preferably, in step S1, the mass ratio of ammonium carbonate to concentrated ammonia solution is (2.5-3.5):1, and the concentration of magnesium chloride solution is 0.05-0.1 mmol / L.

[0011] Preferably, in step S1, the heating temperature is 80°C and the reaction time is 8–16 h; the calcination temperature is 350–450°C and the time is 1.5–2.5 h.

[0012] Preferably, in step S2, the chloroplatinic acid is chloroplatinic acid hexahydrate, and the mass ratio of chloroplatinic acid hexahydrate, polyvinylpyrrolidone, sodium borohydride and magnesium oxide is (9-11):(5-7):(14-16):100.

[0013] Preferably, in step S2, chloroplatinic acid and polyvinylpyrrolidone are added to deionized water and stirred for 0.5 to 1.5 hours, then sodium borohydride is added and stirred for 0.5 to 1.5 hours, and then magnesium oxide is added and stirred for 8 to 12 hours.

[0014] Preferably, in step S2, the thermal decomposition temperature is 250–350°C, the time is 1.5–2.5 h, and the atmosphere is air.

[0015] Secondly, a Pt-PtO x The Mg(OH)2-F catalyst was obtained by the preparation method described in the first aspect.

[0016] Thirdly, as described in the second aspect, Pt-PtO x Application of @Mg(OH)2-F catalyst in the hydrogenation of furfural to prepare furfuryl alcohol.

[0017] The fourth aspect is a method for preparing furfural alcohol by hydrogenation, comprising the following steps:

[0018] Furfural, as described in the second aspect, Pt-PtO x The Mg(OH)2-F catalyst and alcohol are mixed in a closed environment, the air is vented, and then pressure is applied and heated to react.

[0019] Preferably, furfural and Pt-PtO x The mass ratio of the Mg(OH)2-F catalyst is 1:(0.2-0.4), the alcohol includes methanol, ethanol, n-propanol or isopropanol, air is purged using H2 / N2 and pressurized to 1-2 MPa, and the heating temperature is 140-260℃.

[0020] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:

[0021] This invention synthesizes a novel flower-like spherical catalyst, Pt-PtO, using the gas-liquid interface method and the sol-gel method. x @Mg(OH)2-F, efficient conversion of furfural, a biomass platform compound, to furfuryl alcohol was achieved, in which Pt-PtO x The precursor MgO for the @Mg(OH)2-F catalyst is an irregularly stacked, plate-like polyhedron that readily transforms into flower-like spherical Mg(OH)2 in water. The catalyst has a TOF value of 333.96 h⁻¹. -1 The performance of this catalyst is superior to that of most others. Characterization by EXAFS and XPS revealed electronic perturbations between the Pt species and the Mg(OH)2 support, with charge redistribution directly influencing the adsorption behavior during the catalytic process. The Pt-O bonds formed through orbital hybridization alter the charge state of the surface Pt sites, transferring more electrons to the furfural intermediate (C4H3O-CHO*), thereby promoting adsorption. Ultimately, Pt-PtO... x The active sites of the Mg(OH)2-F catalyst are composed of Pt δ+ Lewis acid sites and OH δ- Lewis base site composition, furfural carbonyl group with oxygen atom and Pt in ethanol δ+ The site coordinates to form a six-membered ring transition state, ultimately achieving the reduction of the furfural carbonyl group. Attached Figure Description

[0022] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0023] Figure 1 The images are scanning electron microscope (SEM) images of MgO prepared in Example 1, with (a) and (b) showing different regions, respectively.

[0024] Figure 2 Pt-PtO prepared in Example 1 xScanning electron microscope image of @Mg(OH)2-F, (b) is a magnified view of (a);

[0025] Figure 3 Pt-PtO prepared in Example 1 x Transmission electron microscopy image of @Mg(OH)2-F, (b) is a magnified view of (a);

[0026] Figure 4 Pt-PtO prepared in Example 1 x XRD pattern of @Mg(OH)2-F;

[0027] Figure 5 Pt-PtO prepared in Example 1 x XPS plots of @Mg(OH)2-F: (a) Pt4f, (b) O1s;

[0028] Figure 6 Pt-PtO prepared in Example 1 x (a) EXAFS spectra and (b) Fourier transforms of Mg(OH)2-F and platinum foil;

[0029] Figure 7 (a) Pt-PtO prepared in Example 1 x EXAFS wavelet transform analysis of (a)Mg(OH)2-F and (b) platinum foil;

[0030] Figure 8 Pt-PtO x Flowchart of the reaction of furfural hydrogenation catalyzed by @Mg(OH)2-F. Detailed Implementation

[0031] Currently, industrially applied catalysts suffer from low catalytic activity, limited understanding of catalytic mechanisms, and high processing costs. Adjusting the electron-metal-support interaction (EMSI) in supported metal catalysts is considered the most effective method for regulating electronic structure and improving catalytic performance. However, the charge transfer mechanisms at the electronic level during catalysis remain poorly understood. This invention prepares a Pt-PtO... x @Mg(OH)₂-F catalyst is a promising biomass conversion catalyst. Its preparation process involves gas-liquid interface reactions and a sol-gel method, aiming to construct a catalyst with excellent morphological stability and superior catalytic performance. Pt-PtO x The Mg(OH)₂-F catalyst provides a new theoretical and experimental basis for the efficient conversion and application of biomass resources. Its unique catalyst composition, excellent catalytic activity, and selectivity will provide strong support for research and industrial applications in the field of biomass conversion, and is expected to promote further development and innovation in the biomass energy sector.

[0032] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments and comparative examples.

[0033] Example 1

[0034] The MgO was synthesized using a gas-liquid interface method. 15.0 g of ammonium carbonate and 5.0 g of concentrated ammonia solution were mixed in a 1000 mL beaker. Simultaneously, 0.05 mol of analytical grade MgCl₂·6H₂O was dissolved in a 250 mL glass beaker containing 200 g of ultrapure water. The glass beaker containing the magnesium chloride solution was then sealed inside the beaker containing the ammonium carbonate and concentrated ammonia solution and placed in an oven. After 12 hours, the glass beaker containing the magnesium chloride solution was removed, the precipitate was filtered, washed several times, and then dried in the oven. After grinding, the material was placed in a muffle furnace and calcined at 400 °C for 2 hours to obtain MgO powder. Figure 1 As shown, the MgO powder is an irregular polyhedron formed by stacking nanosheet structures.

[0035] The catalyst was prepared using the sol-gel method. First, 100 mL of deionized water was added to a 250 mL beaker. Then, a mixture of 10.0 mg H₂PtCl₆·6H₂O and 6 mg polyvinylpyrrolidone (PVP) was added and stirred at room temperature. After 1 hour, 15 mg NaBH₄ was added, and stirring continued at room temperature. After another hour, 0.1 g MgO powder was added, and stirring continued overnight. The product was collected by filtration (8000 rpm, 5 minutes) and washed three times each with ethanol and distilled water. The precipitate was collected by centrifugation, dried under vacuum at 80 °C for 24 hours, and then pyrolyzed in air at 300 °C for 2 hours to obtain Pt-PtO. x @Mg(OH)2-F catalyst. For example... Figure 2 and Figure 3 As shown, Pt-PtO x The Mg(OH)2-F catalyst has a flower-like structure, with Pt and Mg(OH)2 exhibiting distinct lattice stripes, exposing the Pt(111) and Mg(OH)2(111) crystal planes, respectively.

[0036] The raw material used for preparing Au@Mg(OH)2-F using the sol-gel method was chloroauric acid trihydrate, and the raw material used for preparing Cu@Mg(OH)2-F was copper chloride dihydrate. Except for the different supporting metal raw materials, the other materials and experimental procedures were the same as those used in Example 1 for Pt-PtO. x The preparation method for the @Mg(OH)2-F catalyst is consistent with that of the Pt@MgO-B catalyst. Additionally, the support used for the Pt@MgO-B preparation is commercially available magnesium oxide, and other materials and experimental procedures are the same as those for the Pt-PtO catalyst in Example 1. xThe preparation method for the Mg(OH)₂-F catalyst is consistent. The above material is prepared for use with Pt-PtO₂. x Compare with @Mg(OH)2-F.

[0037] like Figure 4 As shown, Pt-PtO x The diffraction peaks of @Mg(OH)2-F, Au@Mg(OH)2-F, and Cu@Mg(OH)2-F correspond to Mg(OH)2, while the diffraction peaks of Pt@MgO-B are mainly characteristic peaks of MgO, indicating that the commercial magnesium oxide support did not diffract into Mg(OH)2-F during the reaction. Furthermore, as... Figure 4 As shown, Pt-PtO x The diffraction peaks of @Mg(OH)2-F correspond to those of Mg(OH)2, and diffraction peaks related to MgO also appear, which may be due to the incomplete conversion of the MgO precursor.

[0038] To further investigate the surface chemical composition, metallic composition, and electronic states of the catalyst, Pt-PtO x The Mg(OH)₂-F catalyst was further characterized by X-ray photoelectron spectroscopy (XPS) (e.g.) Figure 5 (As shown). The study of the catalytic system involves complex and diverse interactions, among which the electronic interaction between the supported Pt metal particles and Mg(OH)₂ is crucial, known as electron-metal-support interaction (EMSI). EMSI typically occurs in the interfacial region between the metal and the support, primarily manifested through electronic effects. This interaction leads to electron transfer from the Pt metal nanoparticles, particularly from O atoms in Mg(OH)₂. According to X-ray photoelectron spectroscopy (XPS), Pt exists simultaneously in both +2 and O valence states. This is because Pt typically exists in the +4 oxidation state in H₂PtCl₆, and during the reduction reaction in the preparation process, some Pt(⁴⁺) is reduced to Pt(O), while the remainder remains in the +4 state and binds to oxygen atoms. Pt exhibits the ability to absorb electrons from O atoms in Mg(OH)₂. After receiving some electrons from O atoms, Pt exhibits a lower oxidation state, which can be observed by the position of the O1s peak in the XPS at 531.5 eV, corresponding to the O atom in the lower oxidation state. Therefore, Pt gradually transforms from the +4 oxidation state to the +2 oxidation state. In summary, EMSI promotes electron transfer between Pt and Mg(OH)₂, leading to the transformation of Pt from the +4 oxide state to the +2 oxidation state. This process plays a crucial role in the electronic structure and chemical properties of the catalyst.

[0039] Further verification using EXAFS confirmed the existence of electron transfer between Pt and Mg(OH)₂. Figure 6As shown in (a), Pt-PtO is in the energy range of 11560 eV to 11567 eV. x @Mg(OH)2-F compared to platinum foil (Pt foil), Pt-PtO x @Mg(OH)2-F exhibits a stronger absorption signal. This is due to the interaction between Pt and Mg(OH)2 and the formation of Pt-O bonds. Within this energy range, Pt-PtO... x The absorption intensity of the Mg(OH)2-F sample is higher than that of the Pt foil sample, indicating that there are more absorption states and Pt-O bonds in the sample. Figure 6 (b) in the example is Pt-PtO x Fourier transform of Mg(OH)₂-F catalyst and Pt foil. Approximately on the horizontal axis... At this point, both curves exhibit different peaks, indicating the presence of Pt-Pt bonds within this distance range. Approximately on the horizontal axis... Pt-PtO x @Mg(OH)2-F exhibits distinct characteristic peaks, indicating the presence of Pt-O bonds within this distance range. The appearance of these peaks suggests Pt-PtO x In Mg(OH)₂-F, there is a bond between Pt and O atoms, which is formed by Pt-PtO. x This is caused by electron transfer between Pt and Mg(OH)2 at the interface in @Mg(OH)2-F. Figure 7 In the EXAFS wavelet transform analysis shown, the Pt-O bond appears in Pt-PtO. x The specific abscissa position of the @Mg(OH)2-F catalyst represents the interaction between Pt and O. The presence of Pt-O bonds can be better determined by comparing the wavelet transform spectra of Pt foil.

[0040] Example 2

[0041] Furfural (0.1g) and Pt-PtO from Example 1 were added. x @Mg(OH)2-F catalyst (30 mg) and ethanol (10 mL) were mixed and loaded into the reactor. Air was purged from the reactor using 10% H2 / N2, and finally, the autoclave was pressurized to 2 MPa with 30% H2 / N2. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data. The reacted Pt-PtO... x The Mg(OH)₂-F catalyst was collected, washed, dried, and then recycled for furfural hydrogenation. The results are shown in Table 1. (Pt-PtO)x After five cycles, the conversion and selectivity of the @Mg(OH)₂-F catalyst remained above 99%, with a slight decrease observed from the sixth cycle onwards. Despite the slight decrease in catalyst activity, the furfural conversion remained above 90%, indicating its excellent stability. Figure 4 As shown, the used Pt-PtO x The crystal structure of the Mg(OH)2-F catalyst did not change significantly.

[0042] Table 1. Furfural conversion rate and product selectivity at different cycle numbers

[0043]

[0044] Comparative Example 1

[0045] Furfural (0.1 g) and ethanol (10 mL) were mixed and loaded into a reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the product of the furfural reaction was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0046] Comparative Example 2

[0047] 0.1 g of MgO powder from Example 1 was added to 100 mL of water and stirred overnight. The product was collected by filtration (8000 rpm, 5 minutes) and washed three times each with ethanol and distilled water. The precipitate was collected by centrifugation, dried under vacuum at 80°C for 24 hours, and then pyrolyzed in air at 300°C for 2 hours to obtain Mg(OH)₂.

[0048] Furfural (0.1 g), Mg(OH)₂ (30 mg), and ethanol (10 mL) were mixed and loaded into a reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the product of the furfural reaction was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0049] Comparative Example 3

[0050] Furfural (0.1g) and Pt-PtO from Example 1 were added. x@Mg(OH)2-F catalyst (30 mg) and ethanol (10 mL) were mixed and loaded into the reactor. Air was purged from the reactor using N2, and the autoclave was pressurized to 2 MPa N2. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0051] The furfural conversion rates and product yields in Comparative Examples 2, 1, 2, and 3 are shown in Table 2. The pure Mg(OH)₂ support exhibited low activity with a conversion rate of only 16%. After the introduction of Pt metal, the furfural conversion rate significantly increased to 99.9%, indicating that the introduced metal active sites play a crucial role in furfural conversion. H₂ also plays a vital role as a hydrogen donor; the furfural conversion rate was also low (23.5%) under a N₂ atmosphere.

[0052] Table 2. Furfural conversion rate and product selectivity under different catalysts

[0053]

[0054] Example 3

[0055] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and methanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0056] Example 4

[0057] Furfural (0.1g) and Pt-PtO from Example 1 were added. x @Mg(OH)2-F catalyst (30 mg) and n-propanol (10 mL) were mixed and loaded into the reactor. The air inside the reactor was purged with 10% H2 / N2, and finally, the autoclave was pressurized to 2 MPa with 30% H2 / N2. Then, the reactor was heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was started at 800 r / min and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on the gas chromatography-mass spectrometry data.

[0058] Example 5

[0059] Furfural (0.1g) and Pt-PtO from Example 1 were added. x @Mg(OH)2-F catalyst (30 mg) and isopropanol (10 mL) were mixed and loaded into the reactor. Air was purged from the reactor using 10% H2 / N2, and the autoclave was pressurized to 2 MPa with 30% H2 / N2. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0060] Comparative Example 4

[0061] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and toluene (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0062] Table 3 shows the furfural conversion and product yield under different solvents in Comparative Examples 2-5 and Comparative Example 4. Under H2 atmosphere and with ethanol as the solvent, the furfural conversion was high (99.9%), while the conversion was low (19.2%) in the absence of a hydrogen-donating alcohol (ethanol) during the catalytic reaction with toluene as the solvent. Regarding the choice of alcohol, primary alcohols performed better than secondary alcohols, with ethanol showing the best performance. The low furfural conversion with toluene, which lacks hydrogen-donating ability, indicates that hydrogen-donating alcohols are crucial as solvents.

[0063] Table 3. Furfural conversion rate and product selectivity under different solvents

[0064]

[0065] Pt-PtO x The reaction process of furfural hydrogenation catalyzed by Mg(OH)2-F catalyst under the action of ethanol and H2 is as follows: Figure 8 As shown. The catalytically active sites on the catalyst are typically composed of Lewis acid (LAS) metal ions and Lewis base (LBS) non-metal ions. Pt-PtO x@Mg(OH)₂-F catalysts typically include Pt(δ+) sites and Pt(0) sites. The Pt(δ+) sites act as Lewis acid sites, anchoring the oxygen atoms in the C=O bond of furfural and the CO bond of ethanol. This creates a reaction environment and forms a six-membered ring transition state, promoting the reduction of the carbonyl group via MPV reduction. Two hydrogenation pathways exist here. Specifically, on one hand, hydrogen from H₂ is adsorbed on the surface of the Pt(0) catalyst and dissociates into H radicals. These H radicals participate in the hydrogenation of the oxygen atom in the C=O bond. On the other hand, OH… - As a basic site, it effectively dissociates H radicals and reacts with OH radicals. - The combination of these hydrogen radicals creates more oxygen vacancies. The presence of these vacancies promotes the desorption of H from the OH radical in ethanol, creating a H-radical-rich environment at the reaction site. The synergistic effect of furfural and hydrogen radicals improves the reduction efficiency. H2 plays a crucial role as a hydrogen source; without H2, the conversion rate of furfural is only 23.5%, while with H2, the conversion rate reaches over 99%. Ethanol also plays a vital role as a hydrogen source; without hydrogen-donating alcohol (ethanol), the conversion rate of furfural is only 19.2%, while with ethanol, the conversion rate reaches over 99%. This demonstrates that the synergistic effect of hydrogen radicals from ethanol and H2 enhances the reduction efficiency.

[0066] Example 6

[0067] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and ethanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 140 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0068] Example 7

[0069] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and ethanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 160 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0070] Comparative Example 5

[0071] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and ethanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 120 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 0.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0072] Table 4 shows the furfural conversion rate and product yield at different temperatures in Comparative Examples 2, 6, 7 and 5. The furfural conversion rate increased with increasing temperature.

[0073] Table 4. Furfural conversion rate and product selectivity at different temperatures

[0074]

[0075] Example 8

[0076] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and ethanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 1.0 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0077] Example 9

[0078] Furfural (0.1g) and Pt-PtO from Example 1 were added. x A mixture of Mg(OH)₂-F catalyst (30 mg) and ethanol (10 mL) was loaded into the reactor. Air was purged from the reactor using 10% H₂ / N₂, and the autoclave was pressurized to 2 MPa with 30% H₂ / N₂. The reactor was then heated from room temperature to 180 °C at a rate of 5 °C / min, and the reaction was initiated at 800 rpm and maintained for 1.5 h. During this process, the furfural product was obtained, and the results were obtained based on gas chromatography-mass spectrometry (GC-MS) data.

[0079] Table 5 compares the furfural conversion rate and product yield under different reaction times in Examples 2, 8, and 9. It is shown that extending the reaction time can increase the proportion of furfural converted to furfuryl alcohol.

[0080] Table 5. Furfural conversion rate and product selectivity at different reaction times.

[0081]

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A Pt-PtO x The preparation method of the Mg(OH)2-F catalyst is characterized by, Includes the following steps: S1. Seal an open container containing magnesium chloride solution into a container containing ammonium carbonate and concentrated ammonia solution, heat the reaction, filter the solution in the open container to obtain a precipitate, and calcine the precipitate to obtain magnesium oxide. S2. Chloroplatinic acid hexahydrate and polyvinylpyrrolidone were added to deionized water and stirred. Then sodium borohydride was added and stirred, followed by magnesium oxide and stirred. The precipitate was collected by filtration and thermally decomposed to obtain Pt-PtO. x @Mg(OH)2-F catalyst; The Pt-PtO x The Mg(OH)2-F catalyst is flower-shaped and spherical. The Pt-PtO x The active sites of the Mg(OH)2-F catalyst are composed of Pt δ+ Lewis acid sites and OH δ- Lewis base site composition.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass ratio of ammonium carbonate to concentrated ammonia solution is (2.5~3.5):1, and the concentration of magnesium chloride solution is 0.05~0.1 mmol / L.

3. The preparation method according to claim 1, characterized in that, In step S1, the heating temperature is 80℃ and the reaction time is 8~16 h; the calcination temperature is 350~450℃ and the time is 1.5~2.5 h.

4. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of chloroplatinic acid hexahydrate, polyvinylpyrrolidone, sodium borohydride, and magnesium oxide is (9~11):(5~7):(14~16):

100.

5. The preparation method according to claim 1, characterized in that, In step S2, chloroplatinic acid and polyvinylpyrrolidone are added to deionized water and stirred for 0.5 to 1.5 h, then sodium borohydride is added and stirred for 0.5 to 1.5 h, and then magnesium oxide is added and stirred for 8 to 12 h.

6. The preparation method according to claim 1, characterized in that, In step S2, the thermal decomposition temperature is 250~350℃, the time is 1.5~2.5 h, and the atmosphere is air.

7. A Pt-PtO x @Mg(OH)2-F catalyst, characterized in that, Obtained by the preparation method described in any one of claims 1 to 6.

8. A method for preparing furfural alcohol by hydrogenation, characterized in that, Includes the following steps: Furfural, as described in claim 7, Pt-PtO x The Mg(OH)2-F catalyst and alcohol were mixed in a closed environment, the air was purged, and then pressurized and heated to react. furfural and Pt-PtO x The mass ratio of the Mg(OH)2-F catalyst is 1:(0.2~0.4), the alcohol includes methanol, ethanol, n-propanol or isopropanol, air is purged using H2 / N2 and pressurized to 1~2 MPa, and the heating temperature is 140~260℃.

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