A modified metal nanocatalyst and its preparation method and application

Abstract

A modified metal nanocatalyst, its preparation method and application relate to the technical field of catalysts. The modified metal nanocatalyst is a metal nanocatalyst supported on phosphoric acid (phosphonic acid)-modified titanium oxide or a metal nanocatalyst supported on titanium phosphate (phosphonate). The molecular formula of the metal nanocatalyst supported on titanium phosphate (phosphonate) is M / Ti(RPO4)2, where M is a noble metal and R is H, C1-6 alkane, aryl; the molecular formula of the metal nanocatalyst supported on phosphoric acid (phosphonic acid)-modified titanium oxide is M / Ti a P b O c , where a, b, and c are values between 1 and 5, and the weight ratio of the metal to the carrier is 0.05-50 wt%. The present invention provides a novel nanocatalyst that can overcome the problems of low activity and sulfur poisoning in the deoxygenation of sulfoxide in hydrogen to obtain sulfide. Moreover, the catalyst has high activity, selectivity, and stability, can be recycled, has simple preparation steps, wide application, and good commercial value.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a modified metal nanocatalyst and a preparation method and application thereof. Background Art

[0002] Sulfide is an important chemical intermediate in organic synthesis, biological research, pharmaceutical industry, pesticide synthesis and other processes, and has a wide range of uses. Its production method is mainly to use the corresponding alcohol to sulfurize the highly toxic and smelly sulfur-containing molecules (such as S2Cl2, thiol and thiophenol). The disadvantages of the sulfurization method are low product yield, large amount of waste liquid, dangerous and complicated operation process, etc., and the sulfurization method is difficult to apply to substrates containing multiple active functional groups (such as C=C, C≡C and OH); while the method of obtaining sulfide by catalytic deoxygenation of sulfoxide in hydrogen has the advantages of environmental friendliness, good product quality and high yield, and has been increasingly valued and widely used.

[0003] When catalyzing the deoxidation of sulfoxide in hydrogen to obtain sulfide, one of the most concerned issues is that the metal catalyst is easily poisoned by the product sulfide, thereby reducing the catalyst activity. In recent years, research still has shortcomings such as low catalytic activity and harsh catalytic reaction conditions (high reaction temperature and high activation temperature). There are usually two ways to solve this problem: (1) high-temperature hydrogen reduction before the catalyst is recycled; (2) improving the structural properties of the catalyst to achieve the purpose of not being easily poisoned by the product sulfide; for example, Jpn. Kokai Tokyo Koho, 2015211932, 26Nov 2015 used 4.8wt% Ru / TiO2 as a catalyst to prepare sulfide by catalytic deoxidation, 100℃, H2 pressure 1bar, sulfoxide deoxidation rate TOF = 20h -1 Jpn.Kokai Tokkyo Koho,2018076261,17May 2018Using 0.5wt% Pt / MoO3 as catalyst, the catalyst was pre-reduced for 2 hours at 200℃, sulfide was prepared by catalytic deoxidation, room temperature, H2 pressure 1bar, 500W light, sulfoxide deoxidation rate TOF=53h -1 , the cycle conditions are heating at 400°C in air. The disadvantages of these methods are: low activity and complex and dangerous catalytic cycle process.

[0004] Therefore, a novel catalyst for catalyzing the deoxygenation of sulfoxide in hydrogen is urgently needed to overcome certain technical problems existing in the prior art. Summary of the invention

[0005] In order to overcome the above technical problems, the purpose of the present invention is to provide a new type of nanocatalyst that can overcome the problems of low activity and sulfur poisoning in catalyzing the deoxidation of sulfoxide in hydrogen to obtain sulfide, and the catalyst has high activity, selectivity and stability, simple preparation steps, wide application and good commercial value.

[0006] In order to solve the above problems, the present invention provides a modified metal nanocatalyst and a preparation method and application thereof.

[0007] In one aspect, a modified metal nanocatalyst is provided.

[0008] A modified metal nanocatalyst, wherein the modified metal nanocatalyst is a metal nanocatalyst supported by titanium oxide modified by phosphoric acid (phosphonic acid) or a metal nanocatalyst supported by titanium phosphate (phosphonic acid) salt, wherein the metal nanocatalyst supported by titanium phosphate (phosphonic acid) salt has a molecular formula of M / Ti(RPO4)2, wherein M is a noble metal, and R is H, C1-6 alkane, or aryl; wherein the metal nanocatalyst supported by titanium oxide modified by phosphoric acid (phosphonic acid) has a molecular formula of M / Ti a P b O c , wherein a, b, and c are values ​​between 1 and 5, and the weight ratio of the metal to the support is about 0.05 to about 50 wt %.

[0009] In some embodiments, the weight ratio of the metal to the carrier is about 1.50-about 45wt%, or about 5.5-about 35wt%, or about 8.5-about 25wt%, or about 10.5-about 20wt%; and the carrier is an oxide carrier containing titanium and phosphorus other than precious metals.

[0010] In some embodiments, the precious metal can be a transition metal, such as the first transition series Sc-scandium, Ti-titanium, Cr-chromium, Mn-manganese, Fe-iron, Co-cobalt, Ni-nickel, Cu-copper, Zn-zinc, the second transition series such as Y-yttrium, Zr-zirconium, Nb-niobium, Mo-molybdenum, Tc-technetium, Ru-ruthenium, Rh-rhodium, Pd-palladium, Ag-silver, Cd-cadmium, the third transition series such as Lu-lutetium, Hf-hafnium, W-tungsten, Re-rhenium, Os-osmium, Ir-iridium, Pt-platinum, Au-gold, Hg-mercury, etc.

[0011] In some embodiments, the precious metal includes at least one of Pt, Pd, Rh, Ru, Ir, Fe, Co, and Ni.

[0012] In some embodiments, the C1-6 alkane is methyl, ethyl, propyl, isopropyl, butyl, etc., and the aryl is phenyl or benzyl.

[0013] In some embodiments, the modified metal nanocatalyst is Pt / Ti(PhPO3)2, Ru / Ti(HPO4)2, Rh / Ti(HPO4)2, Pd / Ti(HPO4)2 or Pt / Ti(HPO4)2, etc.

[0014] In some embodiments, a method for preparing the titanium oxide-supported metal nanocatalyst modified by phosphoric acid (phosphonic acid) as described in the first aspect is provided, which comprises mixing the titanium oxide-supported metal nanocatalyst, a hydrocarbon solvent, and chlorides of phosphorus and phosphine, and stirring the resulting mixture in a dry atmosphere for a certain period of time to obtain the titanium oxide-supported metal nanocatalyst modified by phosphoric acid (phosphonic acid).

[0015] In some embodiments, the titanium oxide includes TiO2, Ti2O3, TiO x Y, at least one of oxidized TiC. (Y refers to other carriers that form a mixed phase with Ti, such as: Al2O3, SiO2, VO2, CrO2, MnO2, Fe2O3, CoO, NiO, CuO, ZnO, SnO2, MoO3, etc.)

[0016] In some embodiments, the metal includes at least one of Pt, Pd, Rh, Ru, Ir, Fe, Co, and Ni.

[0017] In some embodiments, the titanium oxide-supported metal nanocatalyst may be selected from Pt / TiO2, Pd / TiO2, Ru / TiO2, Ni / TiO2,

[0018] In some embodiments, the chloride of phosphorus or phosphine includes at least one of PCl5, POCl3, PhPOCl2, EtPOCl2, PhPCl2, EtPCl2, PhOPOCl2, EtOPOCl2, Ph2POCl, Et2POCl, Ph2PCl, Et2PCl, (PhO)2POCl, and (EtO)2POCl.

[0019] In some embodiments, the hydrocarbon solvent can be selected from one or more of n-hexane, heptane, petroleum ether, benzene or toluene.

[0020] In some embodiments, a method for preparing a titanium phosphate (phosphonate) salt-supported metal nanocatalyst is provided, comprising:

[0021] Step (1) adding a titanium oxide carrier, a hydrocarbon solvent and a chloride of phosphorus or phosphine in a reaction bottle in sequence, stirring and modifying the mixture in a dry atmosphere for a certain period of time to obtain a titanium oxide carrier modified with phosphoric acid (phosphonic acid);

[0022] Step (2) adding a noble metal salt solution to the phosphoric acid (phosphonic acid) modified titanium oxide carrier obtained in step (1), stirring and dispersing, and then adding urea to react at about 70° C. to about 100° C. to obtain a phosphoric acid (phosphonic acid) modified titanium oxide supported metal nanocatalyst.

[0023] In some embodiments, the preparation method includes sequentially adding titanium phosphate (phosphonate), hydrocarbon solvent and noble metal salt solution into a reaction bottle, loading the metal on the carrier by urea precipitation method or the like, and obtaining a phosphate (phosphonate) loaded metal nanocatalyst.

[0024] In some embodiments, the chloride of phosphorus or phosphine includes at least one of PCl5, POCl3, PhPOCl2, EtPOCl2, PhPCl2, EtPCl2, PhOPOCl2, EtOPOCl2, Ph2POCl, Et2POCl, Ph2PCl, Et2PCl, (PhO)2POCl, and (EtO)2POCl.

[0025] In some embodiments, the titanium oxide includes TiO2, Ti2O3, TiO x Y, at least one of oxidized TiC. (Y refers to other carriers that form a mixed phase with Ti, such as: Al2O3, SiO2, VO2, CrO2, MnO2, Fe2O3, CoO, NiO, CuO, ZnO, SnO2, MoO3, etc.)

[0026] In some embodiments, the metal includes at least one of Pt, Pd, Rh, Ru, Ir, Fe, Co, and Ni.

[0027] In some embodiments, the titanium phosphate (phosphonate) salt includes at least one of Ti(HPO4)2·xH2O, Ti(HPO4)2, TiP2O7, Ti(H2PO4)3, TiPO4, Ti(OH)PO4, Ti(PO4Ph)2·xH2O, Ti(PO4Ph)2·xH2O, Ti(PO3Et)2·xH2O, and Ti(PO3Et)2·xH2O. (X=0-2)

[0028] In some embodiments, the hydrocarbon solvent can be selected from one or more of n-hexane, heptane, petroleum ether, benzene or toluene.

[0029] In some embodiments, after adding urea, the reaction is carried out at about 80° C. to about 90° C. to obtain a phosphoric acid (phosphonic acid)-modified titanium oxide-supported metal nanocatalyst.

[0030] In some embodiments, the weight ratio of the titanium oxide-supported metal nanocatalyst to the chloride of phosphorus or phosphine is 0.05-5wt%, and the chloride of phosphorus or phosphine can be a chlorine compound such as POCl3, PCl5, EtOPOCl2, etc. The reaction temperature in the reactor is about 0-about 80°C, preferably about 40-about 60°C, and the reaction time is about 0.5h-5h, preferably 1h-2h.

[0031] The catalyst prepared by the invention is mainly used for catalyzing the deoxidation of sulfoxide in hydrogen to prepare sulfide, and the sulfoxide is diphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, 4,4'-dimethoxydiphenyl sulfoxide, phenyl methyl sulfoxide, 4-methylphenyl methyl sulfoxide, 4-methoxyphenyl methyl sulfoxide, butyl sulfoxide, benzyl sulfoxide, cyclobutyl sulfoxide, phenyl chloromethyl sulfoxide, sulindac, omeprazole, fenbendazole, sulfinpyrazone, ethiprole, fipronil and the like.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] In order to overcome the problem of catalyzing the deoxidation of sulfoxide in hydrogen to obtain sulfide, the catalytic activity is provided to be more than 10 times, and a high reaction temperature is not required. The present invention optimizes the catalyst itself to achieve low-cost, high-stability and high-quality catalysts. The present invention provides a novel nanocatalyst that can overcome the problems of low activity and sulfur poisoning in catalyzing the deoxidation of sulfoxide in hydrogen to obtain sulfide, and the catalyst has high activity, selectivity and stability, simple preparation steps, wide application and good commercial value.

[0034] (1) The present invention can directly modify commercial titanium dioxide-supported metal catalysts, and the preparation process is simple;

[0035] (2) Phosphoric acid on the catalyst acts as a bridge. The dissociated hydrogen on Pt overflows to the surface through phosphoric acid, and sulfoxide is deoxidized on the titanium oxide support, isolating the dissociated hydrogen and the deoxidation reaction, resulting in high catalytic activity.

[0036] (3) The metal catalyst supported by titanium dioxide modified by phosphoric acid in the present invention has a stable chemical structure, which makes the metal catalyst resistant to sulfur poisoning, has stable deoxidation activity, has a long service life, and can be recycled many times;

[0037] (4) Excellent catalytic activity: The metal nanocatalysts supported by titanium oxide modified by phosphoric acid (phosphonic acid) and the metal nanocatalysts supported by titanium phosphate (phosphonic acid) salts catalyze the deoxidation of sulfoxide in hydrogen to prepare sulfide. The sulfoxide conversion rate is as high as 100%. The activity is very high and high-purity sulfide can be obtained. The selectivity can reach more than 99%.

[0038] (5) There is no need to use high-temperature hydrogen reduction to prevent sulfur poisoning, which reduces costs. More importantly, the batch stability is good, which further improves product quality assurance and reduces process costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The infrared spectra of Ph-P-Pt / TiO2, PhO-P-Pt / TiO2, P-Pt / TiO2, Pt / TiO2, P-Pd / TiO2 and Pd / TiO2 prepared in Example 1 were treated with Ar and H2 in sequence. The infrared observation and analysis showed that there were phosphate groups on the catalyst surface. After hydrogen treatment, the 2000cm -1 The infrared signal of phosphate is enhanced while that of ordinary titanium dioxide supported catalyst is not.

[0040] Figure 2 The solid-state nuclear magnetic resonance phosphorus spectra of P-Pt / TiO2 and Ph-P-Pt / TiO2 prepared in Example 1 are shown. The solid-state nuclear magnetic resonance observation and analysis of phosphorus on the catalyst

[0041] Figure 3 The XRD spectra of P-Pt / TiO2, P-Pd / TiO2, P-Ru / TiO2, P-Rh / TiO2 and Pt / TiO2 prepared in Example 1 are shown;

[0042] Figure 4 XRD spectra of Ph-P-Pt / TiO2, PhO-P-Pt / TiO2, EtO-P-Pt / TiO2 and Pt / TiO2 prepared in Example 1 are shown

[0043] Figure 5 The solid state NMR phosphorus spectrum of Pt / Ti(HPO4)2 prepared in Example 2 is shown;

[0044] Figure 6 The XRD spectra of Pt / Ti(HPO4)2, Pd / Ti(HPO4)2, Ru / Ti(HPO4)2 and Rh / Ti(HPO4)2 prepared in Example 2 are shown in FIG.

[0045] Figure 7 Cyclic stability curve of deoxygenation of diphenyl sulfoxide to diphenyl sulfide catalyzed by Pt / Ti(HPO4)2 catalyst. Specific embodiments

[0046] Example 1: Titanium oxide supported metal nanocatalyst modified by phosphoric acid (phosphonic acid)

[0047] 1. Synthesis of phosphoric acid modified Pt / TiO2 catalyst (P-Pt / TiO2)

[0048] Weigh 1g Pt / TiO2 and mix it with 30mL n-hexane, stir evenly, add 0.1mL phosphorus oxychloride, and stir at 60℃ for 2 hours. Centrifuge the obtained gray product, wash it three times with n-hexane, ethanol and water respectively, and dry it at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, you can get the gray powder of phosphoric acid-modified Pt / TiO2 catalyst.

[0049] 2. Synthesis of phosphoric acid modified Pd / TiO2 catalyst (P-Pd / TiO2)

[0050] Weigh 1g Pd / TiO2 and mix it with 30mL n-hexane, stir evenly, add 0.1mL phosphorus oxychloride, and stir at 60℃ for 2 hours. Centrifuge the obtained gray product, wash it three times with n-hexane, ethanol and water respectively, and dry it at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, you can get the gray powder of phosphoric acid-modified Pd / TiO2 catalyst.

[0051] 3. Synthesis of Ru / TiO2 catalyst modified with phosphoric acid (P-RuTiO2)

[0052] Weigh 1g Ru / TiO2 and mix with 30mL n-hexane, stir evenly, add 0.1mL phosphorus oxychloride, and stir at 60℃ for 2 hours. Centrifuge the obtained gray product, wash three times with n-hexane, ethanol and water respectively, and dry at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, the gray powder of phosphoric acid-modified Ru / TiO2 catalyst can be obtained.

[0053] 4. Synthesis of phosphoric acid-modified Rh / TiO2 catalyst (P-Rh / TiO2)

[0054] Weigh 1g Rh / TiO2 and mix with 30mL n-hexane, stir evenly, add 0.1mL phosphorus oxychloride, and stir at 60℃ for 2 hours. Centrifuge the obtained gray product, wash three times with n-hexane, ethanol and water respectively, and dry at 90℃. Transfer the obtained gray powder to a muffle furnace and heat at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, the gray powder of phosphoric acid-modified Rh / TiO2 catalyst can be obtained.

[0055] 5. Synthesis of Ni / TiO2 catalyst modified with phosphoric acid (P-Ni / TiO2)

[0056] Weigh 1g Ni / TiO2 and mix it with 30mL n-hexane, stir evenly, add 0.1mL phosphorus oxychloride, and stir at 60℃ for 2 hours. The obtained gray product is centrifuged, washed three times with n-hexane, ethanol and water respectively, and dried at 90℃. The obtained gray powder is transferred to a muffle furnace and heated at 250℃ for 2 hours. After it is naturally cooled, it is transferred to a tube furnace and heated at 250℃ in 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it is naturally cooled, it is transferred to a tube furnace and heated at 250℃ for 2 hours. After it is naturally cooled, a gray powder of phosphoric acid-modified Ni / TiO2 catalyst is obtained.

[0057] 6. Synthesis of Pt / TiO2 Catalyst Modified by Ethyl Phosphate (EtO-P-Pt / TiO2)

[0058] Weigh 1g Pt / TiO2 and mix with 30mL n-hexane, stir evenly, add 0.1mL ethyl dichlorophosphate, and stir at 60℃ for 2 hours. Centrifuge the obtained gray product, wash three times with n-hexane, ethanol and water respectively, and dry at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, the gray powder of Pt / TiO2 catalyst modified by ethyl phosphate can be obtained.

[0059] 7. Synthesis of Pt / TiO2 Catalyst Modified by Ethylphosphonic Acid (Et-P-Pt / TiO2)

[0060] Weigh 1g Pt / TiO2 and mix with 30mL n-hexane, stir evenly, add 0.1mL ethylphosphonic acid dichloride, stir and react at 60℃ for 2 hours. Centrifuge the obtained gray product, wash three times with n-hexane, ethanol and water respectively, and dry at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, the gray powder of Pt / TiO2 catalyst modified by ethylphosphonic acid can be obtained.

[0061] 8. Synthesis of phosphoric acid modified Pt / TiO2 catalyst (PhO-P-Pt / TiO2)

[0062] Weigh 1g TiO2 and mix it with 30mL n-hexane, stir evenly, add 0.5mL phosphorus oxychloride, and stir and react at 60℃ for 2 hours. The obtained gray product was centrifuged, washed three times with n-hexane, ethanol and water respectively, and dried at 90℃. The obtained gray powder was transferred to a muffle furnace and heated at 250℃ for 2 hours. After it was cooled naturally, the white powder of P-TiO2 was obtained. Weigh 1g P-TiO2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1mol / L) of potassium tetrachloroplatinate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. The obtained white powder was transferred to a muffle furnace and heated at 250℃ for 2 hours. After it is cooled naturally, it is transferred to a tube furnace and heated at 250° C. in a 5% H 2 / Ar (gas flow rate 40 mL / min) atmosphere for 2 hours. After it is cooled naturally, a gray powder of phosphoric acid-modified Pt / TiO 2 catalyst is obtained.

[0063] 9. Synthesis of Pt / TiO2 Catalyst Modified by Phenylphosphonic Acid (Ph-P-Pt / TiO2)

[0064] Weigh 1g Pt / TiO2 and mix with 30mL n-hexane, stir evenly, add 0.1mL phenylphosphonic acid dichloride, stir and react at 60℃ for 2 hours. Centrifuge the obtained gray product, wash three times with n-hexane, ethanol and water respectively, and dry at 90℃. Transfer the obtained gray powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃ 5wt% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, the gray powder of Pt / TiO2 catalyst modified by ethylphosphonic acid can be obtained.

[0065] 10. Synthesis of phosphoric acid modified Pt / TiO2 catalyst (Pt / P-TiO2)

[0066] Weigh 1g TiO2 and mix it with 30mL n-hexane, stir evenly, add 0.5mL phosphorus oxychloride, and stir and react at 60℃ for 2 hours. The obtained gray product was centrifuged, washed three times with n-hexane, ethanol and water respectively, and dried at 90℃. The obtained gray powder was transferred to a muffle furnace and heated at 250℃ for 2 hours. After it was cooled naturally, the white powder of P-TiO2 was obtained. Weigh 1g P-TiO2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1mol / L) of potassium tetrachloroplatinate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. The obtained white powder was transferred to a muffle furnace and heated at 250℃ for 2 hours. After it is cooled naturally, it is transferred to a tube furnace and heated at 250° C. in a 5% H 2 / Ar (gas flow rate 40 mL / min) atmosphere for 2 hours. After it is cooled naturally, a gray powder of phosphoric acid-modified Pt / TiO 2 catalyst is obtained.

[0067] Example 2: Phosphate-supported metal nanocatalysts

[0068] 1. Synthesis of Pt / Ti(HPO4)2 catalyst

[0069] Weigh 1g Ti(HPO4)2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1 mol / L) of potassium tetrachloroplatinate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. Transfer the obtained white powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tubular furnace and heat it at 250℃ in 5% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, a gray powder of Pt / Ti(HPO4)2 catalyst can be obtained.

[0070] 2. Synthesis of Pd / Ti(HPO4)2 catalyst

[0071] Weigh 1g Ti(HPO4)2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1 mol / L) of sodium tetrachloropalladate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. Transfer the obtained white powder to a muffle furnace and heat it at 250℃ for 2 hours. After it is cooled naturally, transfer it to a tubular furnace and heat it at 250℃ in a 5% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it is cooled naturally, a gray powder of Pd / Ti(HPO4)2 catalyst can be obtained.

[0072] 3. Synthesis of Rh / Ti(HPO4)2 catalyst

[0073] Weigh 1g Ti(HPO4)2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1 mol / L) rhodium acetate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. Transfer the obtained white powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tube furnace and heat it at 250℃5% H2 / Ar (gas flow rate 40 mL / min) atmosphere for 2 hours. After it cools naturally, you can get the gray powder of Rh / Ti(HPO4)2 catalyst.

[0074] 4. Synthesis of Ru / Ti(HPO4)2 catalyst

[0075] Weigh 1g Ti(HPO4)2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1 mol / L) of ruthenium trichloride aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. Transfer the obtained white powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tubular furnace and heat it at 250℃ in 5% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, you can get a gray powder of Ru / Ti(HPO4)2 catalyst.

[0076] 5. Synthesis of Pt / Ti(PhPO3)2 catalyst

[0077] Weigh 1g Ti(PhPO3)2 and place it in a 200mL reaction bottle, add 80mL water and ultrasonically disperse it evenly. Add 0.5mL (0.1 mol / L) of potassium tetrachloroplatinate aqueous solution during stirring, stir and disperse for 10 minutes, add 0.2g urea during stirring, stir and disperse for 10 minutes, and heat at 90℃ for 6 hours. After the reaction bottle is cooled naturally, centrifuge and disperse it in water, repeat washing three times, and dry at 90℃. Transfer the obtained white powder to a muffle furnace and heat it at 250℃ for 2 hours. After it cools naturally, transfer it to a tubular furnace and heat it at 250℃ in 5% H2 / Ar (gas flow rate 40mL / min) atmosphere for 2 hours. After it cools naturally, you can get a gray powder of Pt / Ti(PhPO3)2 catalyst.

[0078] Example 3 Characterization of the catalysts prepared in Examples 1 and 2

[0079] Figure 1 The infrared spectra of Ph-P-Pt / TiO2, PhO-P-Pt / TiO2, P-Pt / TiO2, Pt / TiO2, P-Pd / TiO2 and Pd / TiO2 prepared in Example 1 were treated in situ with Ar and H2 respectively. Infrared observation and analysis showed that there were phosphate groups on the surface of the catalyst. After hydrogen treatment, the infrared signal of phosphate groups at 2000cm-1 was enhanced, while that of ordinary titanium dioxide-supported catalysts was not enhanced.

[0080] Figure 2 The solid-state nuclear magnetic resonance phosphorus spectra of P-Pt / TiO2 and Ph-P-Pt / TiO2 prepared in Example 1 are shown. The solid-state nuclear magnetic resonance observation and analysis of phosphorus on the catalyst

[0081] Figure 3 The XRD spectra of P-Pt / TiO2, P-Pd / TiO2, P-Ru / TiO2, P-Rh / TiO2 and Pt / TiO2 prepared in Example 1 are shown;

[0082] Figure 4 XRD spectra of Ph-P-Pt / TiO2, PhO-P-Pt / TiO2, EtO-P-Pt / TiO2 and Pt / TiO2 prepared in Example 1 are shown

[0083] Figure 5 The solid state NMR phosphorus spectrum of Pt / Ti(HPO4)2 prepared in Example 2 is shown;

[0084] Figure 6 The XRD spectra of Pt / Ti(HPO4)2, Pd / Ti(HPO4)2, Ru / Ti(HPO4)2 and Rh / Ti(HPO4)2 prepared in Example 2 are shown in FIG.

[0085] Figure 7Cyclic stability curve of deoxygenation of diphenyl sulfoxide to diphenyl sulfide catalyzed by Pt / Ti(HPO4)2 catalyst.

[0086] Example 4: Catalytic application of phosphoric acid (phosphonic acid) modified titanium oxide supported metal nanocatalyst

[0087] Weigh 0.05g of commercial 1% Pt / TiO2, 1% Pd / TiO2, 1% Ru / TiO2, and 1% Rh / TiO2, respectively, and name them as test groups 1, 2, 3, and 4, respectively, add them to a 20mL reaction bottle, then add 0.101g of diphenyl sulfoxide, add 5mL of toluene as solvent, react at 1bar H2 and 60℃ for 1 hour, take samples, and use gas chromatography analysis with internal standard method to determine the performance of different catalysts in catalyzing the deoxygenation of diphenyl sulfoxide to prepare diphenyl sulfide. The specific situation is shown in Table 1.

[0088] Weigh 0.05 g of phosphoric acid-modified 1% Pt / TiO2, 1% Pd / TiO2, 1% Ru / TiO2, and 1% Rh / TiO2, respectively, and name them as test groups 5, 6, 7, and 8, respectively, and add them to a 20 mL reaction bottle, then add 0.101 g of diphenyl sulfoxide, add 5 mL of toluene as a solvent, react at 1 bar H2 and 60°C for 1 hour, take samples, and use gas chromatography analysis with the internal standard method to determine the performance of different catalysts in catalyzing the deoxidation of diphenyl sulfoxide to prepare diphenyl sulfide. The specific situation is shown in Table 1.

[0089] Table 1 Reaction results of deoxygenation of diphenyl sulfoxide to diphenyl sulfide catalyzed by different catalysts

[0090]

[0091] Example 4: Catalytic application of phosphate-supported metal catalysts

[0092] Weigh 0.05 g of 1% Pt / Ti(HPO4)2 and 0.5 mol of sulfoxide substrates (diphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, 4,4'-dimethoxydiphenyl sulfoxide, phenyl methyl sulfoxide, 4-methylphenyl methyl sulfoxide, 4-methoxyphenyl methyl sulfoxide, phenyl chloromethyl sulfoxide, benzyl sulfoxide, cyclobutyl sulfoxide, butyl sulfoxide, sulindac, omeprazole, sulfinpyrazone, ethiprole, fipronil) respectively, name the test groups 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 respectively, add them into a 20 mL reaction bottle, then add 5 mL of deuterated chloroform as solvent, react for several hours at 1 bar H2 and 60°C, take samples, and use nuclear magnetic resonance analysis to determine the performance of the catalyst in catalyzing the preparation of sulfides from different sulfoxides. Specific circumstances such as Figure 1 shown.

[0093] Table 2 Reaction results of sulfide deoxidation catalyzed by phosphate-supported metal catalysts

[0094]

[0095]

[0096] Example 5: Reuse of Pt / Ti(HPO4)2

[0097] Weigh 0.05g of 1% Pt / Ti(HPO4)2 and 0.101g of diphenyl sulfoxide respectively, add them into a 20mL reaction bottle, then add 5mL of toluene as solvent, react for several hours at 1bar H2 and 60℃, take samples, wash with ethanol three times, dry at 250℃ for 2 hours, reuse under the same conditions, and take samples respectively. Use internal standard method and gas chromatography to determine the performance of the catalyst in catalyzing the deoxygenation of diphenyl sulfoxide to prepare diphenyl sulfide. The specific situation is as follows Figure 7 shown.

Claims

1. Use of a modified metal nanocatalyst in catalyzing the deoxidation of sulfoxide in hydrogen to prepare sulfide, characterized in that: The modified metal nanocatalyst is a metal nanocatalyst supported by titanium phosphate or titanium phosphonate as a carrier. The metal nanocatalyst supported by titanium phosphate or titanium phosphonate has a molecular formula of M / Ti(RPO4)2, wherein M is a noble metal, the noble metal is Pt or Pd, R is H, C1-6 alkane, or aromatic group, and the weight ratio of the metal to the carrier is 0.05-50wt%.

2. The use according to claim 1, characterized in that: The C1-6 alkane is methyl, ethyl, propyl, isopropyl or butyl, and the aryl is phenyl or benzyl.

3. The use according to claim 1, characterized in that: The modified metal nanocatalyst is Pd / Ti(HPO4)2 or Pt / Ti(HPO4)2.

4. The use according to any one of claims 1 to 3, characterized in that: The sulfoxide is diphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, 4,4'-dimethoxydiphenyl sulfoxide, phenyl methyl sulfoxide, 4-methylphenyl methyl sulfoxide, 4-methoxyphenyl methyl sulfoxide, butyl sulfoxide, benzyl sulfoxide, cyclobutyl sulfoxide, phenyl chloromethyl sulfoxide, sulindac, omeprazole, fenbendazole, sulfinpyrazone, ethiprole or fipronil.

Images