A diatomic catalyst supported on a metal-organic framework material and its preparation and application

Abstract

Preparation of a diatomic catalyst supported on a metal-organic framework (MOF) and its application in the hydrogen esterification of olefins. This invention provides a diatomic catalyst supported on the ethylenediaminetetraacetic acid (EDTA)-modified MOF material MIL-101(Cr), with a Ru single atom as the active site and a second metal Fe, Co, or Ni single atom as a promoter, for the hydrogen esterification of olefins to prepare organic carboxylic acid esters. Under certain temperature, pressure, and the action of the catalyst, olefins, CO, and alcohols can be directly converted into organic carboxylic acid esters, exhibiting high activity, selectivity, and stability.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to the preparation of a ruthenium and iron / cobalt / nickel bimetallic catalyst supported on a metal-organic framework material MIL-101(Cr) modified with ethylenediaminetetraacetic acid (EDTA) and its application in the preparation of organic carboxylic acid esters by olefin hydrogen esterification. Background Technology

[0002] Organic carboxylic acid esters are an important class of organic synthetic intermediates with significant applications in food, pharmaceuticals, cosmetics, coatings, dyes, and other manufacturing sectors. Simultaneously, carboxylic acid esters are also important electrolyte solvents, exhibiting excellent solubility and stability, and are widely used in energy fields such as batteries and supercapacitors, with considerable development potential. Therefore, the production of organic carboxylic acid esters is of great significance both in chemical organic synthesis and at the industrial level.

[0003] Olefin hydrogen esterification can produce organic carboxylic acid esters in one step, with 100% atom economy, in line with the concept of green, environmentally friendly and sustainable development (see Equation 2). This reaction uses CO as the carbonyl source and alcohols as nucleophiles. Under the catalysis of active metals such as Ni, Co, Fe, Pd, Ru, Rh or Ir, organic carboxylic acid esters with one more carbon atom can be directly prepared, producing both straight-chain and branched products.

[0004]

[0005] Equation 2: Reaction equation for the preparation of organic carboxylic acid esters by olefin hydrogen esterification

[0006] Research on the preparation of organic carboxylic acid esters via olefin hydrogen esterification has long focused on homogeneous systems. Among these, hydrogen esterification systems represented by non-noble metals such as Fe, Co, and Ni suffer from harsh reaction conditions and low activity. Olefin hydrogen esterification systems catalyzed by noble metals, particularly Pd, have been extensively studied due to their high activity, selectivity, and mild reaction conditions; however, they require the addition of acid promoters and organophosphorus ligands, leading to problems such as equipment corrosion and poor economic efficiency. Furthermore, homogeneous reactions suffer from difficulties in separating the catalyst from the product and their recycling, hindering industrial development. Therefore, developing a heterogeneous catalytic system with high activity and selectivity comparable to homogeneous catalysis, while also achieving good stability and easy catalyst separation, is of significant research importance.

[0007] Here, we propose a bimetallic solid heterogeneous catalyst supported on the metal-organic framework material MIL-101(Cr) modified with ethylenediaminetetraacetic acid (EDTA), comprising ruthenium, iron, cobalt, and nickel, for the preparation of organic carboxylic acid esters via olefin hydrogen esterification. This catalytic system exhibits high activity and selectivity. By utilizing the MIL-101(Cr) metal-organic framework as a support, its large pore size and high specific surface area are fully utilized to improve mass transfer efficiency, and its abundant Lewis acid sites facilitate reactant enrichment. Simultaneously, the anchoring of the active metal with EDTA significantly enhances catalyst stability. The absence of additional acidic promoters mitigates the corrosiveness of the reaction system, greatly reducing equipment investment costs. Furthermore, the heterogeneous system allows for easy separation of the catalyst from the reaction system, reducing separation costs and demonstrating broad industrial application prospects. Summary of the Invention

[0008] A diatomic catalyst supported on a metal-organic framework material:

[0009] The catalyst consists of an active component and a support. The active component is ruthenium, and the second metal promoter is one or more of iron, cobalt, or nickel. The support is a metal-organic framework material modified with ethylenediaminetetraacetic acid (MIL-101(Cr)), named MIL-101(Cr)-EDTA. The active component is loaded on the support.

[0010] The catalyst contains ruthenium at a mass content of 0.5-2%, preferably 1.0-1.5%, and the second metal additive, iron / cobalt / nickel, contains iron / cobalt / nickel at a mass content of 0.1-15%, preferably 1-5%. The remainder is a metal-organic framework material MIL-101(Cr)-EDTA modified with ethylenediaminetetraacetic acid, which is composed of chromium, carbon, hydrogen, oxygen and nitrogen.

[0011] "Dual-atom catalysts (DACs)" refers to bimetallic catalysts in which the active metal is a single atom, and is simply called a dual-atom catalyst.

[0012] The catalyst is prepared by dissolving a precursor of ruthenium and a second metal (one or more of iron, cobalt or nickel) in a solvent to obtain a corresponding metal precursor solution. The precursor solution is then loaded onto a metal-organic framework material MIL-101(Cr)-EDTA support modified with ethylenediaminetetraacetic acid by low-temperature ultrasonic wet impregnation. Finally, the catalyst is obtained by rotary evaporation and drying.

[0013] The temperature of the low-temperature ultrasonic wet impregnation is maintained at 0-20℃, preferably 10-15℃, and the ultrasonic duration is 0.5-3.0h, preferably 1.0-1.5h; the rotary evaporation drying temperature is 40-70℃, preferably 55-65℃, and the rotary evaporation duration is 0.5-1.5h, preferably 0.8-1.2h.

[0014] The ruthenium precursors are ruthenium chloride (RuCl3), ruthenium bromide (RuBr3), ruthenium iodide (RuI3), ruthenium acetate (Ru(OAc)3), ruthenium hexaammonium chloride ([Ru(NH3)6]Cl3), ruthenium acetylacetone (Ru(acac)3), ruthenium nitrosyl sulfate ([Ru(NO)]2(SO4)3), ruthenium dichloride pentane complex ruthenium chloride ([Ru(NH3)5Cl]Cl2), and ruthenium dichloro(pentamethylcyclopentadienyl) ruthenium ([(C 10 H 15 RuCl2] n One or more of the following: ruthenium chloride (RuCl3), ruthenium bromide (RuBr3), and ruthenium acetate (Ru(OAc)3); preferably one or more of these.

[0015] The iron precursors are ferric chloride (FeCl3), ferric bromide (FeBr3), ferric iodide (FeI3), ferric sulfate (Fe2(SO4)3), ferric nitrate (Fe(NO3)3), ferric acetylacetone (Fe(acac)3), ferric phosphate (FePO4), ferric pyrophosphate (Fe4(P2O7)3), ferric tartrate (Fe2(C4H4O6)3), and ferric ethoxide (C6H 15 FeO3), ferric citrate (C6H5FeO7), ferric perchlorate (FeCl3O) 12 ), ferric 2-ethylhexanoate (C 24 H 45 FeO6), ferric p-toluenesulfonate ((CH3C6H4SO3)3Fe), tri(hexafluoroacetylacetone)ferric (C 15 H3F 18 Ferric trifluoromethanesulfonate (C3F9FeO9S3), ferric diethyldithiocarbamate (C 15 H 30 One or more of the following: FeN3S6; preferably one or more of the following: ferric chloride (FeCl3), ferric bromide (FeBr3), ferric sulfate (Fe2(SO4)3), and ferric nitrate (Fe(NO3)3);

[0016] The cobalt precursors are cobalt chloride (CoCl2), cobalt fluoride (CoF2), cobalt bromide (CoBr2), cobalt iodide (CoI2), cobalt acetate (Co(OAc)2), cobalt nitrate (Co(NO3)2), cobalt sulfate (CoSO4), cobalt acetylacetonate (Co(acac)2), cobalt phosphate (Co3(PO4)2), and cobalt phthalocyanine (C 32 H 16 CoN8), cobalt isopropoxide (C6H) 14 CoO2), cobalt thiocyanate (C2CoN2S2), cobalt citrate (Co3(C6H5O7)2), cobalt tetraphenylporphyrin (C 44 H 28 CoN4), cobalt stearate (C 36 H 70 One or more of the following: Cobalt(O)4; preferably one or more of the following: Cobalt(Cl2), Cobalt(Br2), Cobalt(OAc)2, Cobalt(NO3)2, and Cobalt(SO4);

[0017] The nickel precursors are nickel chloride (NiCl2), nickel bromide (NiBr2), nickel iodide (NiI2), nickel acetate (Ni(OAc)2), nickel nitrate (Ni(NO3)2), nickel sulfate (NiSO4), nickel phosphate (Ni3(PO4)2), nickel oxalate (NiC2O4), nickel acetylacetone (Ni(acac)2), and nickel cyclohexanebutyrate (C... 20 H 34 NiO4), nickel phthalocyanine (C) 32 H 16 N8Ni), nickel trifluoromethanesulfonate (C2F6NiO6S2), nickel perchlorate (Cl2H 12 NiO 14 Nickel naphthenate (C) 22 H 14 One or more of nickel(NiO4) and nickel(C2H6NiO6) are preferred; one or more of nickel(Cl2) chloride, nickel(Br2) bromide, nickel(OAc)2, nickel(NO3)2, and nickel(NiSO4) are preferred.

[0018] The solvent for dissolving the metal precursor is one or more of water, ethanol, dichloromethane, tetrahydrofuran, acetone, toluene, and N,N-dimethylformamide; preferably one or more of water, ethanol, and acetone.

[0019] The molar concentration of ruthenium in the ruthenium precursor solution is 10–125 mmol / L, preferably 50–75 mmol / L;

[0020] The molar concentration of one or more of the precursors, namely iron, cobalt or nickel, in the solution is 0.5 to 17 mmol / L, preferably 1.6 to 9.6 mmol / L.

[0021] The active component of the catalyst, ruthenium, and one or more of the second metal promoters, iron, cobalt, or nickel, are all atomically dispersed on a metal-organic framework material MIL-101(Cr)-EDTA carrier modified with ethylenediaminetetraacetic acid.

[0022] The preparation method of the metal-organic framework material modified by ethylenediaminetetraacetic acid is as follows: a certain mass of disodium ethylenediaminetetraacetic acid dihydrate is dissolved in a certain volume of ultrapure water, metal-organic framework material MIL-101(Cr) is added, and then the mixture is heated and stirred to react. After filtration, water washing and vacuum drying, the metal-organic framework material MIL-101(Cr)-EDTA carrier modified by ethylenediaminetetraacetic acid is obtained.

[0023] The mass ratio of the disodium ethylenediaminetetraacetate dihydrate to the metal-organic framework material MIL-101(Cr) is 0.1 / 1 to 30 / 1, preferably 1 / 1 to 10 / 1; the mass ratio of the disodium ethylenediaminetetraacetate dihydrate to water is 0.02 / 1 to 0.1 / 1, preferably 0.04 / 1 to 0.06 / 1.

[0024] The heating reaction temperature is 40–90°C, preferably 60–80°C; the reaction time is 12–36 h, preferably 20–24 h.

[0025] The drying process is vacuum drying, with a vacuum drying temperature of 50–180°C, preferably 80–150°C; and a drying time of 6–24 hours, preferably 10–15 hours.

[0026] The preparation method of the metal-organic framework material MIL-101(Cr) is as follows:

[0027] Using chromium ions from chromium salts as metal nodes, terephthalic acid as organic ligands, and acid or base as mineralizing agents, a suspension is formed in water by thorough stirring. The suspension is then transferred to a hydrothermal reactor and subjected to a high-temperature hydrothermal reaction to form a solid. After washing with a hot solvent and drying, the metal-organic framework material MIL-101(Cr) can be obtained.

[0028] The chromium salt is one or more of chromium nitrate, chromium chloride, chromium sulfate, chromium acetate, and chromium acetylacetonate, preferably one or more of chromium nitrate, chromium acetate, and chromium acetylacetonate.

[0029] The reactant ratio is such that the molar ratio of chromium metal ions to organic ligands ranges from 1 / 10 to 10 / 1, preferably from 0.5 / 1 to 2 / 1; the concentration of chromium metal ions in water is 0.0001 to 0.0002 mol / L, preferably from 0.00013 to 0.00018 mol / L.

[0030] The mineralizing agent is one or more of hydrofluoric acid, nitric acid, benzoic acid, acetic acid, 2-methylimidazolium, 4-methylimidazolium, 2-ethyl-4-methylimidazolium, sodium acetate, and tetramethylammonium hydroxide; preferably one or more of hydrofluoric acid and nitric acid; the concentration of nitric acid is 0.21–0.24 mol / L; the concentration of hydrofluoric acid is 0.12–0.14 mol / L.

[0031] The hydrothermal reaction temperature is 150–220°C, preferably 200–220°C; the hydrothermal duration is 6.0–24 h, preferably 8–10 h.

[0032] The hot solvent is one or more of N,N-dimethylformamide, ethanol, methanol, ammonium fluoride aqueous solution, and chloroform, preferably one or more of N,N-dimethylformamide and ethanol; the heating temperature is 50-80℃, preferably 60-80℃; the washing time is 6-20h, preferably 10-15h.

[0033] Application of the metal-organic framework material-supported diatomic catalyst in the catalytic hydrogen esterification of olefins to prepare organic carboxylic acid esters.

[0034] In the presence of ruthenium supported on ethylenediaminetetraacetic acid-modified metal-organic framework material MIL-101(Cr) and iron / cobalt / nickel bimetallic solid heterogeneous catalyst, alcohols are used as reactants and solvents to prepare organic carboxylic acid esters by hydrogen esterification with olefins and CO under certain temperature and pressure.

[0035] The reaction temperature is 140–250℃, preferably 160–220℃; the reaction pressure is 0.05–20.0 MPa, preferably 0.5–5 MPa.

[0036] The raw material olefin is one or more of O1 to O7 in the compound shown in Formula 1;

[0037]

[0038] Formula 1. Types of raw material olefins

[0039] The raw material alcohol is one or more of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, benzyl alcohol, and phenylethanol.

[0040] The reaction is carried out in a fixed bed, trickle bed, slurry bed, or batch reactor; when using a fixed bed or trickle bed, the liquid hourly space velocity is 0.01–20.0 h⁻¹. -1 Preferably 1-5 hours -1 The air space velocity is 100–20,000 h⁻¹. -1 Preferably 500-2000h -1 ;

[0041] The molar ratio of ruthenium metal to alcohol in the solid heterogeneous catalyst is 0.00001:1 to 0.001:1, preferably 0.00005:1 to 0.0005:1; the molar ratio of ruthenium metal to olefin feedstock in the solid heterogeneous catalyst is 0.0001:1 to 0.05:1, preferably 0.0005:1 to 0.005:1; the molar ratio of ruthenium metal to CO in the solid heterogeneous catalyst is 0.00001:1 to 0.001:1, preferably 0.00005:1 to 0.0005:1.

[0042] The beneficial effects of this invention are as follows:

[0043] Compared with traditional techniques for preparing organic carboxylic acid esters through olefin hydrogen esterification, the catalytic system of this invention requires no additional acid promoters or organophosphorus ligands, greatly alleviating the system's corrosion problem and making it more economical and environmentally friendly. Using the metal-organic framework material MIL-101(Cr) as a support facilitates reactant enrichment and improves mass transfer efficiency. The ethylenediaminetetraacetic acid ion can firmly bind to the active metal ruthenium and the second metal (iron / cobalt / nickel), and is highly dispersed on the support surface in single-atom form, which is beneficial for the synergistic effect between the two metals and gives the catalyst high activity, selectivity, and stability. Furthermore, the solid heterogeneous catalyst of this invention has significant advantages in catalyst recovery and recycling, as well as the separation of the catalyst from reactants and products, and has broad prospects for industrial application. Attached Figure Description

[0044] Figure 1 The X-ray diffraction (XRD) patterns of catalyst Ru1-Co1 / MIL-101(Cr)-EDTA-01 (I) in Example 1, catalyst Ru1-Fe1 / MIL-101(Cr)-EDTA-01 (V) in Example 8, catalyst Ru1-Ni1 / MIL-101(Cr)-EDTA-01 (VⅠⅠ) in Example 10, support MIL-101(Cr)-EDTA-01 and support MIL-101(Cr) in Comparative Example 1, and standard X-ray diffraction (XRD) pattern simulating MIL-101(Cr); Figure 1X-ray diffraction (XRD) patterns of MIL-101(Cr)-Simulated, MIL-101(Cr), MIL-101(Cr)-EDTA, Ru1-Co1 / MIL-101(Cr)-EDTA, Ru1-Fe1 / MIL-101(Cr)-EDTA, and Ru1-Ni1 / MIL-101(Cr)-EDTA catalysts;

[0045] Figure 2 Scanning electron microscope (SEM) images of (a) carrier MIL-101(Cr) and (b) carrier MIL-101(Cr)-EDTA-01 of Comparative Example 1; Figure 2 (a) Scanning electron microscope (SEM) images of MIL-101(Cr) and (b) MIL-101(Cr)-EDTA catalysts;

[0046] Figure 3 Transmission electron microscopy (TEM) images of (a) MIL-101(Cr), (b) MIL-101(Cr)-EDTA, (c) Ru1 / MIL-101(Cr)-EDTA, (d) Ru1-Co1 / MIL-101(Cr)-EDTA, (e) Ru1-Fe1 / MIL-101(Cr)-EDTA, and (f) Ru1-Ni1 / MIL-101(Cr)-EDTA catalysts. Figure 3 Transmission electron microscopy (TEM) images of (a) support MIL-101(Cr), (b) support MIL-101(Cr)-EDTA-01 in Comparative Example 1, (c) catalyst Ru1 / MIL-101(Cr)-EDTA-01 in Comparative Example 2 (IX), (d) catalyst Ru1-Co1 / MIL-101(Cr)-EDTA-01 in Example 1 (I), (e) catalyst Ru1-Fe1 / MIL-101(Cr)-EDTA-01 in Example 8 (V), and (f) catalyst Ru1-Ni1 / MIL-101(Cr)-EDTA-01 in Example 10 (VII).

[0047] Figure 4 High-angle annular dark-field scanning transmission (HAADF-STEM) image of catalyst Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) in Example 1; Figure 4 High-angle annular dark-field scanning transmission (HAADF-STEM) image of the Ru1-Co1 / MIL-101(Cr)-EDTA catalyst;

[0048] Table 2 shows the elemental analysis results of the carriers MIL-101(Cr)-EDTA-01 and MIL-101(Cr) in Comparative Example 1.

[0049] Discussion of the figures: To demonstrate the single-atom dispersion of the active metal component in the catalysts described in this application, the following catalysts were characterized by XRD, SEM, TEM, HADDF-STEM and elemental analysis: Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) in Example 1, Ru1-Fe1 / MIL-101(Cr)-EDTA-01(V) in Example 8 and Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VⅠⅠ) in Example 10.

[0050] like Figure 1 As shown, compared with the standard XRD pattern of simulated MIL-101(Cr), both the support MIL-101(Cr) and the support MIL-101(Cr)-EDTA show good matching, proving that the support MIL-101(Cr) was successfully synthesized; the introduction of EDTA did not change its crystal structure. Furthermore, compared with the supports MIL-101(Cr) and MIL-101(Cr)-EDTA, no sharp peaks of metals Ru, Fe, Co, or Ni were found in the XRD patterns of the catalysts Ru1-Co1 / MIL-101(Cr)-EDTA, Ru1-Fe1 / MIL-101(Cr)-EDTA, and Ru1-Ni1 / MIL-101(Cr)-EDTA. Therefore, it can be preliminarily concluded that the metal atoms on the above bimetallic catalysts did not agglomerate and may exhibit a single-point or single-atom dispersion state.

[0051] like Figure 2 As shown, SEM images of the carriers MIL-101(Cr) and MIL-101(Cr)-EDTA indicate that both exhibit octahedral morphology; simultaneously, Figure 3 TEM images also showed that the surfaces of the carrier MIL-101(Cr) and MIL-101(Cr)-EDTA remained unchanged after the introduction of EDTA, indicating that EDTA entered the pores of MIL-101(Cr). Furthermore, elemental analysis in Table 2 confirmed the presence of nitrogen, further supporting the introduction of EDTA.

[0052] like Figure 3 As shown, no metal clusters were found in the high-resolution TEM images of the catalysts Ru1-Fe1 / MIL-101(Cr)-EDTA, Ru1-Co1 / MIL-101(Cr)-EDTA, and Ru1-Ni1 / MIL-101(Cr)-EDTA. Therefore, it can be inferred that the active components, metals Ru and Fe, Co, or Ni, may be dispersed as single atoms.

[0053] like Figure 4As shown in the HADDF-STEM image of the catalyst Ru1-Co1 / MIL-101(Cr)-EDTA, metal Ru and Co are distributed on the support in the form of single atoms, and no obvious clusters are observed on the surface (the bright spots are chromium-oxygen clusters of metal nodes in the metal-organic framework material of the support). It can be determined that metal Ru and Co are dispersed as single atoms. Detailed Implementation

[0054] The following embodiments illustrate, but are not limited to, the content to be protected by this invention.

[0055] To better illustrate the superiority of ethylenediaminetetraacetic acid (EDTA)-modified metal-organic framework material MIL-101(Cr) supported on ruthenium and iron / cobalt / nickel bimetallic catalysts in olefin hydrogen esterification reactions and the differences in process conditions for olefin hydrogen esterification reactions, the following specific implementation examples are presented. EEDTA-modified MIL-101(Cr) supported on ruthenium and iron / cobalt / nickel bimetallic catalysts were prepared under different conditions, denoted as Ru1-M1 / MIL-101(Cr)-EDTA, where M represents Fe, Co, or Ni, and the subscript 1 indicates a single atom. For example: Ru1-Co1 / MIL-101(Cr)-EDTA-01(I), where the Arabic numeral "01" represents the preparation conditions of the EDTA-modified MIL-101(Cr)-EDTA support, and the Roman numeral "I" represents the preparation conditions of the bimetallic catalyst supported on the support. The following examples use a batch reactor as an example; the same logic applies to fixed bed, trickle bed, and slurry bed reactors. In the following examples, firstly, with the reaction process conditions and metal loading fixed (wherein, the mass content of metal Ru was 1.0% and the mass content of the second metal promoter Fe, Co, or Ni was 0.6%), variables such as the type of mineralizer and the ratio of disodium EDTA dihydrate (EDTA-2Na·2H2O) to metal-organic framework material MIL-101(Cr) in the preparation method of the catalyst support ethylenediaminetetraacetic acid modified metal-organic framework material MIL-101(Cr)-EDTA were discussed (Examples 1-4); variables such as the type of metal precursor, the type of precursor of the second metal promoter Fe, Co, or Ni, and the loading (with the mass content of metal Ru fixed at 1.0%) in the method of supporting bimetallic Ru1-M1 (M represents Fe, Co, or Ni) catalyst were discussed (Examples 5-11); secondly, with the catalyst fixed, factors such as temperature, pressure, type of olefin, and type of alcohol in the batch reaction process were investigated (Examples 12-24). Carrier preparation method: 4.0 g of chromium nitrate nonahydrate (Cr(NO3)3·9H2O) and 1.66 g of terephthalic acid (H2BDC) were weighed into a beaker. A certain mass of mineralizing agent (concentrated nitric acid HNO3 or hydrofluoric acid HF) was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker and stirred for 0.5 h. The mixture was then transferred to a hydrothermal reactor and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide and ethanol at 80 °C (the solvent was changed twice, and each washing lasted 3 h). Finally, the mixture was dried in a vacuum oven at 80 °C for 12 h to obtain the metal-organic framework material MIL-101(Cr) (where the chromium content is 20%, obtained by ICP-OES characterization).A certain mass of disodium ethylenediaminetetraacetate dihydrate (EDTA-2Na·2H2O) was weighed into a round-bottom flask, and 150 mL of ultrapure water was added. After stirring thoroughly to form a homogeneous solution, 1.0 g of metal-organic framework material MIL-101(Cr) was added. The mixture was heated and stirred in an oil bath at 60 °C for 24 h. After filtration, washing with water, and vacuum drying at 80 °C for 12 h, the metal-organic framework material MIL-101(Cr)-EDTA modified with ethylenediaminetetraacetate was obtained. Catalyst preparation method: A certain amount of ruthenium and iron, cobalt or nickel metal precursors were weighed and dissolved in 10 mL of ultrapure water, and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g of the above ethylenediaminetetraacetic acid modified metal-organic framework material MIL-101(Cr)-EDTA support was weighed and ultrasonically dispersed in 50 mL of ultrapure water; the above precursor metal solution was added dropwise to the support dispersion suspension by low-temperature ultrasonic wet impregnation for 30 min, then stirred at room temperature overnight, and finally dried by rotary evaporation at 60 °C for 1 h to obtain Ru1-M1 / MIL-101(Cr)-EDTA catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (the mass content of Ru was measured to be 1.0% by ICP-OES). The batch reaction process is as follows: Weigh 0.15g of catalyst and 5.0g of alcohol into a 50mL reactor. After purging with inert gas three times, introduce olefin (ethylene, propylene or butene) gas (or add a certain mass of liquid olefin before loading) and carbon monoxide (CO) gas at a certain pressure. Heat to a certain temperature and react for a certain time. Then quench the reaction with ice water. Take the reaction solution for gas chromatography analysis and calculate the olefin conversion rate and the yield of the target product.

[0056] Example 1

[0057] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0058] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the Ru mass content was 1.0% and the Co mass content was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0059] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0060] Example 2

[0061] Preparation of MIL-101(Cr)-EDTA-02 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 0.5 g HF was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-02 carrier.

[0062] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-02(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-02 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-02(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the Ru mass content was 1.0% and the Co mass content was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0063] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-02(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl acetate yield were calculated. The results are shown in Table 1.

[0064] Example 3

[0065] Preparation of MIL-101(Cr)-EDTA-03 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 and 70 mL ultrapure water were weighed to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 5.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0066] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-03(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were weighed and dissolved in 10 mL of ultrapure water, and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g of MIL-101(Cr)-EDTA-03 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, and then stirred at room temperature overnight. Finally, it was dried by rotary evaporation at 60 °C for 1 h to obtain Ru1-Co1 / MIL-101(Cr)-EDTA-03(I) catalyst, and then calcined at 200 °C with argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0067] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-03(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0068] Example 4

[0069] Preparation of MIL-101(Cr)-EDTA-04 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 1.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0070] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-04(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-04 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-04(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0071] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-04(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0072] Example 5

[0073] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0074] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(II) catalyst: 0.0504 g of ruthenium chloride and 0.01 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(II) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.25%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0075] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(II) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0076] Example 6

[0077] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0078] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(III) catalyst: 0.0504 g of ruthenium chloride and 0.12 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(III) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.85%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0079] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(III) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0080] Example 7

[0081] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0082] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(IV) catalyst: 0.0504 g Ru(OAc)3 and 0.12 g Co(OAc)2 were weighed and dissolved in 10 mL of ultrapure water, and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g MIL-101(Cr)-EDTA-01 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(IV) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0083] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(IV) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0084] Example 8

[0085] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0086] Preparation of Ru1-Fe1 / MIL-101(Cr)-EDTA-01(V) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of FeCl3·6H2O were weighed and dissolved in 10 mL of ultrapure water, and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Fe1 / MIL-101(Cr)-EDTA-01(V) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Fe was 0.6%; TEM and HADDF-STEM determined that Ru and Fe were single-atom dispersed).

[0087] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Fe1 / MIL-101(Cr)-EDTA-01(V) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0088] Example 9

[0089] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0090] Preparation of Ru1-Fe1 / MIL-101(Cr)-EDTA-01(VI) catalyst: 0.0504 g Ru(OAc)3 and 0.05 g Fe(NO3)3·9H2O were weighed and dissolved in 10 mL of ultrapure water, respectively, and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g MIL-101(Cr)-EDTA-01 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain Ru1-Fe1 / MIL-101(Cr)-EDTA-01(VI) catalyst. Before the reaction, the catalyst was calcined at 200 °C for 2 h under argon atmosphere (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Fe was 0.6%; TEM and HADDF-STEM determined that Ru and Fe were single-atom dispersed).

[0091] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Fe1 / MIL-101(Cr)-EDTA-01(VI) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion and methyl propionate yield were calculated. The results are shown in Table 1.

[0092] Example 10

[0093] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0094] Preparation of Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VII) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of NiCl2·6H2O were weighed and dissolved in 10 mL of ultrapure water, respectively, and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VII) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Ni was 0.6%; TEM and HADDF-STEM determined that Ru and Ni were single-atom dispersed).

[0095] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VII) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0096] Example 11

[0097] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0098] Preparation of Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VIIⅠ) catalyst: 0.0504 g Ru(OAc)3 and 0.05 g Ni(OAc)2·4H2O were weighed and dissolved in 10 mL of ultrapure water, respectively, and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g MIL-101(Cr)-EDTA-01 support was weighed and ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VIIⅠ) catalyst. Before the reaction, the catalyst was calcined at 200 °C for 2 h under argon atmosphere (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Ni was 0.6%; TEM and HADDF-STEM determined that Ru and Ni were single-atom dispersed).

[0099] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Ni1 / MIL-101(Cr)-EDTA-01(VIIⅠ) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0100] Example 12

[0101] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0102] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0103] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 150 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0104] Example 13

[0105] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0106] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0107] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.5 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 190 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0108] Example 14

[0109] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0110] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0111] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.5 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0112] Example 15

[0113] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0114] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0115] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 2.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0116] Example 16

[0117] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0118] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0119] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of ethanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and ethyl propionate yield were calculated. The results are shown in Table 1.

[0120] Example 17

[0121] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0122] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0123] Ethylene hydrogenation reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of propanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and propyl propionate yield were calculated. The results are shown in Table 1.

[0124] Example 18

[0125] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0126] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0127] Propylene hydrogen esterification reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C3H6 and 1.0 MPa CO gas (the molar ratio of olefin to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0128] Example 19

[0129] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0130] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0131] The process of n-butene hydrogen esterification: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa of n-butene and 1.0 MPa of CO gas (molar ratio of olefin to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0132] Example 20

[0133] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0134] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature. Finally, it was dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES analysis showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%).

[0135] The process of pentene hydrogen esterification: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst, 14 mmol of n-pentene, and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, CO gas at 1.0 MPa (molar ratio of olefin to CO was 1 / 1) was introduced, and the temperature was raised to 170 °C. After reacting for 6 h, the reaction was quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0136] Example 21

[0137] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0138] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0139] Hexene hydrogen esterification reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst, 14 mmol of n-hexene, and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, CO gas at 1.0 MPa (molar ratio of olefin to CO was 1 / 1) was introduced, and the temperature was raised to 170 °C. After reacting for 6 h, the reaction was quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0140] Example 22

[0141] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0142] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0143] Cyclohexene hydrogen esterification reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst, 14 mmol of cyclohexene, and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, CO gas at 1.0 MPa (molar ratio of olefin to CO was 1 / 1) was introduced, and the temperature was raised to 170 °C. After reacting for 6 h, the reaction was quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0144] Example 23

[0145] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0146] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0147] Octene hydrogen esterification reaction process: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst, 14 mmol of n-octene, and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, CO gas at 1.0 MPa (molar ratio of olefin to CO was 1 / 1) was introduced, and the temperature was raised to 170 °C. After reacting for 6 h, the reaction was quenched with ice water. The reaction solution was collected for gas chromatography analysis, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0148] Example 24

[0149] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0150] Preparation of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst: 0.0504 g of ruthenium chloride and 0.05 g of cobalt chloride were dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution. 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed that the mass content of Ru was 1.0% and the mass content of Co was 0.6%; TEM and HADDF-STEM determined that Ru and Co were single-atom dispersed).

[0151] The process of nonene hydrogen esterification: 0.15 g of Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) catalyst, 14 mmol of nonene, and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, CO gas at 1.0 MPa (molar ratio of olefin to CO was 1 / 1) was introduced, and the temperature was raised to 170 °C. After reacting for 6 h, the reaction was quenched with ice water. The reaction solution was analyzed by gas chromatography, and the olefin conversion rate and the yield of the target product were calculated. The results are shown in Table 1.

[0152] Comparative Example 1

[0153] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0154] Ethylene hydrogenation reaction process: 0.15 g of MIL-101(Cr)-EDTA-01(I) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0155] Comparative Example 2

[0156] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0157] Preparation of Ru1 / MIL-101(Cr)-EDTA-01(IX) catalyst: 0.0504 g of ruthenium chloride was dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Ru1 / MIL-101(Cr)-EDTA-01(IX) catalyst. The catalyst was calcined at 200 °C under argon for 2 h before the reaction (the mass content of Ru was determined to be 1.0% by ICP-OES).

[0158] Ethylene hydrogenation reaction process: 0.15 g of Ru1 / MIL-101(Cr)-EDTA-01(IX) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0159] Comparative Example 3

[0160] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0161] Preparation of Co1 / MIL-101(Cr)-EDTA-01(X) catalyst: 0.1 g of cobalt chloride was dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g of MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Co1 / MIL-101(Cr)-EDTA-01(X) catalyst. The catalyst was calcined at 200 °C under argon for 2 h before the reaction (ICP-OES analysis showed a Co content of 1.5%).

[0162] Ethylene hydrogenation reaction process: 0.15 g of Co1 / MIL-101(Cr)-EDTA-01(X) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0163] Comparative Example 4

[0164] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0165] Preparation of Fe1 / MIL-101(Cr)-EDTA-01(XI) catalyst: 0.1 g FeCl3·6H2O was dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain the Fe1 / MIL-101(Cr)-EDTA-01(XI) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES showed a Fe mass content of 1.5%; TEM indicated that the Fe was a single-atom dispersion).

[0166] Ethylene hydrogenation reaction process: 0.15 g of Fe1 / MIL-101(Cr)-EDTA-01(XI) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gas (molar ratio of C2H4 to CO was 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0167] Comparative Example 5

[0168] Preparation of MIL-101(Cr)-EDTA-01 support: 4.0 g Cr(NO3)3·9H2O and 1.66 g H2BDC were weighed into a beaker. 1.40 g concentrated HNO3 was weighed and dissolved in 70 mL of ultrapure water to prepare a homogeneous solution, which was then poured into the beaker. The mixture was stirred for 0.5 h, transferred to a hydrothermal reactor, and heated in an oven at 220 °C for 8 h. After naturally cooling to room temperature, the mixture was washed sequentially with N,N-dimethylformamide at 80 °C and ethanol. Finally, it was dried in a vacuum oven at 80 °C for 12 h to obtain MIL-101(Cr). Weigh 10.0 g of EDTA-2Na·2H2O into a round-bottom flask, add 150 mL of ultrapure water, and stir thoroughly to form a homogeneous solution. Then add 1.0 g of MIL-101(Cr), heat and stir in an oil bath at 60 °C for 24 h, filter, wash with water, and vacuum dry at 80 °C for 12 h to obtain the MIL-101(Cr)-EDTA-01 carrier.

[0169] Preparation of Ni1 / MIL-101(Cr)-EDTA-01(XII) catalyst: 0.10 g NiCl2·6H2O was dissolved in 10 mL of ultrapure water and stirred thoroughly to form a homogeneous metal precursor solution; 1.0 g MIL-101(Cr)-EDTA-01 support was ultrasonically dispersed in 50 mL of ultrapure water. The above precursor metal solution was added dropwise to the support dispersion suspension for 30 min, then stirred overnight at room temperature, and finally dried by rotary evaporation at 60 °C for 1 h to obtain Ni1 / MIL-101(Cr)-EDTA-01(XII) catalyst. Before the reaction, the catalyst was calcined at 200 °C under argon for 2 h (ICP-OES determined the Ni mass content to be 1.5%; TEM indicated that Ni was a single-atom dispersion).

[0170] Ethylene hydrogenation reaction process: 0.15 g of Ni1 / MIL-101(Cr)-EDTA-01(XII) catalyst and 5.0 g of methanol were weighed and added to a 50 mL reactor. After purging with argon three times, 1.0 MPa C2H4 and 1.0 MPa CO gases (C2H4 to CO molar ratio of 1 / 1) were introduced. The temperature was raised to 170 °C, and the reaction was carried out for 6 h. The reaction was then quenched with ice water. The reaction solution was analyzed by gas chromatography, and the ethylene conversion rate and methyl propionate yield were calculated. The results are shown in Table 1.

[0171] An application example is the use of the prepared catalyst in the olefin hydrogen esterification reaction to prepare organic carboxylic acid esters.

[0172] Using the catalysts prepared in Examples 1-24 and Comparative Examples 1-5, corresponding carboxylic acid ester products were prepared according to the reaction process conditions in their respective examples. The conversion rate of the raw olefin, the yield of the carboxylic acid ester product, and the positive and negative ratios of the target product are shown in Table 1.

[0173] Table 1 Results of the preparation of organic carboxylic acid esters by olefin hydrogen esterification

[0174]

[0175]

[0176] The results showed that Examples 1-4 presented the results of applying the ethylenediaminetetraacetic acid-modified metal-organic framework material MIL-101(Cr)-EDTA support prepared under different conditions to the same reaction conditions after loading Ru and a second metal promoter, Fe, Co, or Ni (with a fixed loading amount). The results indicated changes in the type of mineralizer and the ratio of EDTA-2Na·2H2O to MIL-101(Cr). The results showed that the support prepared with concentrated nitric acid exhibited higher catalytic activity after metal loading. Changing the ratio of EDTA-2Na·2H2O to MIL-101(Cr) did not significantly affect the catalytic activity. To ensure the overall stability of the catalytic system, the MIL-101(Cr)-EDTA-01(I) support was used in the study. Examples 5-11 show the results of preparing MIL-101(Cr)-EDTA supported bimetallic Ru1-M1 (M represents Fe, Co, or Ni) catalysts under different conditions and applying them to the same reaction conditions. These results involve changing the type of metal precursor, the type of the second metal promoter (Fe, Co, or Ni), and the loading amount (with a fixed Ru mass content of 1.0%). The results show that, at the same Ru loading, the olefin conversion increases with increasing second metal promoter loading, but the promoting efficiency decreases. At the same Ru and second metal promoter loading (Fe, Co, or Ni), different precursor types have no significant effect on the reaction activity. Therefore, Ru1-Co1 / MIL-101(Cr)-EDTA-01(I) is still considered the optimal catalyst. Examples 12-24 show the results of applying it to the olefin hydrogen esterification reaction to prepare organic carboxylic acid esters under different reaction conditions, involving changes in temperature, pressure, reactant alcohols, and substrate olefins. Factors such as temperature, pressure, type of alcohol, and type of olefin in the batch reactor process were investigated. The results show that high temperature is beneficial to the hydrogen esterification reaction of olefins, but the stability of the catalyst needs to be considered comprehensively. Under a certain partial pressure of ethylene, the increase of CO partial pressure does not significantly promote the conversion of ethylene. In addition, low carbon number olefins and low carbon number alcohols are beneficial to the hydrogen esterification reaction of olefins to prepare organic carboxylic acid esters. Comparative Example 1 shows that the pure support MIL-101(Cr)-EDTA-01(I) has no catalytic activity in this reaction system. Comparative Examples 2-5 show that in the Ru1 / MIL-101(Cr)-EDTA-01(I) catalyst, metal Ru is the active center of the reaction system, while metals Fe, Co, or Ni have no catalytic activity when present alone. In addition, the activity is low when only metal Ru is present, while the appropriate addition of a second metal promoter Fe, Co, or Ni can further improve the reaction activity.

[0177] Table 2. Elemental analysis results of carrier MIL-101(Cr) and carrier MIL-101(Cr)-EDTA

[0178]

Claims

1. A diatomic catalyst supported on a metal-organic framework material, characterized in that: The catalyst consists of an active component and a support. The active component is ruthenium, and the second metal promoter is one or more of iron, cobalt, or nickel. The support is a metal-organic framework material MIL-101(Cr) modified with ethylenediaminetetraacetic acid (EDTA), named MIL-101(Cr)-EDTA. The active component is loaded on the support. The catalyst contains 0.5-2% ruthenium by mass, the second metal additive iron / cobalt / nickel by mass is 0.1-15%, and the remainder is MIL-101(Cr)-EDTA, a metal-organic framework material modified with ethylenediaminetetraacetic acid, which is composed of chromium, carbon, hydrogen, oxygen and nitrogen. The catalyst is prepared by dissolving ruthenium and the precursor of the second metal in a solvent to obtain the corresponding metal precursor solution. The precursor solution is loaded onto the metal-organic framework material MIL-101(Cr)-EDTA support modified with ethylenediaminetetraacetic acid by low-temperature ultrasonic wet impregnation. Finally, the catalyst is obtained by rotary evaporation. The temperature of the low-temperature ultrasonic wet impregnation is maintained at 0~20 ℃, the ultrasonic duration is 0.5~3.0 h, the rotary evaporation drying temperature is 40~70 ℃, and the rotary evaporation duration is 0.5~1.5 h.

2. The diatomic catalyst supported on a metal-organic framework material according to claim 1, characterized in that: The catalyst contains 1.0-1.5% ruthenium by mass, and the second metal additive, iron / cobalt / nickel, contains 1-5% ruthenium by mass. The temperature of the low-temperature ultrasonic wet impregnation is maintained at 10-15 °C, and the ultrasonic duration is 1.0-1.5 h. The rotary evaporation drying temperature is 55-65 °C, and the rotary evaporation duration is 0.8-1.2 h.

3. A method for preparing the catalyst according to claim 1, characterized in that: The catalyst is prepared by dissolving ruthenium and a second metal precursor in a solvent to obtain a corresponding metal precursor solution. The precursor solution is then loaded onto a metal-organic framework material MIL-101(Cr)-EDTA supported by ethylenediaminetetraacetic acid (EDTA) via low-temperature ultrasonic wet impregnation. Finally, the catalyst is dried by rotary evaporation. The second metal is one or more of iron, cobalt, or nickel. The temperature of the low-temperature ultrasonic wet impregnation is maintained at 0~20 ℃, the ultrasonic duration is 0.5~3.0 h, the rotary evaporation drying temperature is 40~70 ℃, and the rotary evaporation duration is 0.5~1.5 h.

4. The method for preparing the catalyst according to claim 3, characterized in that: The temperature of the low-temperature ultrasonic wet impregnation is maintained at 10~15 ℃, and the ultrasonic duration is 1.0~1.5 h; the rotary evaporation drying temperature is 55~65 ℃, and the rotary evaporation duration is 0.8~1.2 h.

5. The method for preparing the catalyst according to claim 3, characterized in that: The ruthenium precursor is one or more of ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium acetate, hexaammineruthenium chloride, ruthenium acetylacetonate, ruthenium nitrite sulfate, ruthenium dichloride pentane complex, and dichloro(pentamethylcyclopentadienyl)ruthenium; the iron precursor is ferric chloride, ferric bromide, ferric sulfate, ferric nitrate, ferric acetylacetonate, ferric phosphate, ferric pyrophosphate, ferric tartrate, ferric ethoxide, ferric citrate, ferric perchlorate, and 2- Ferric ethylhexanoate, ferric p-toluenesulfonate, ferric tri(hexafluoroacetylacetone), ferric trifluoromethanesulfonate, and ferric diethyldithiocarbamate are selected as one or more of the following: the cobalt precursor is cobalt chloride, cobalt fluoride, cobalt bromide, cobalt iodide, cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt acetylacetone, cobalt phosphate, cobalt phthalocyanine, cobalt isopropoxide, cobalt thiocyanate, cobalt citrate, cobalt tetraphenylporphyrin, and cobalt stearate. The nickel precursor is one or more of the following: nickel chloride, nickel bromide, nickel iodide, nickel acetate, nickel nitrate, nickel sulfate, nickel phosphate, nickel oxalate, nickel acetylacetone, nickel cyclohexanebutyrate, nickel phthalocyanine, nickel trifluoromethanesulfonate, nickel perchlorate, nickel naphthenate, and nickel glycolate. The solvent for dissolving the metal precursor is one or more of the following: water, ethanol, dichloromethane, tetrahydrofuran, acetone, toluene, and N,N-dimethylformamide. The molar concentration of ruthenium in the ruthenium precursor solution is 10–125 mmol / L. The molar concentration of one or more of the precursors, namely iron, cobalt, or nickel, in the solution is 0.5 to 17 mmol / L.

6. The method for preparing the catalyst according to claim 5, characterized in that: The ruthenium precursor is one or more of ruthenium chloride, ruthenium bromide, and ruthenium acetate; The iron precursor is one or more of ferric chloride, ferric bromide, ferric sulfate, and ferric nitrate. The cobalt precursor is one or more of cobalt chloride, cobalt bromide, cobalt acetate, cobalt nitrate, and cobalt sulfate; The nickel precursor is one or more of nickel chloride, nickel bromide, nickel acetate, nickel nitrate, and nickel sulfate; The solvent for dissolving the metal precursor is one or more of water, ethanol, and acetone. The molar concentration of ruthenium in the ruthenium precursor solution is 50–75 mmol / L; The molar concentration of one or more of the precursors, namely iron, cobalt, or nickel, in the solution is 1.6 to 9.6 mmol / L.

7. The method for preparing the catalyst according to claim 3, characterized in that: The active component of the catalyst, ruthenium, and one or more of the second metal promoters, iron, cobalt, or nickel, are all atomically dispersed on a metal-organic framework material MIL-101(Cr)-EDTA carrier modified with ethylenediaminetetraacetic acid.

8. The preparation method according to claim 3, characterized in that: The preparation method of the metal-organic framework material modified by ethylenediaminetetraacetic acid is as follows: dissolve the disodium ethylenediaminetetraacetic acid dihydrate in water, add the metal-organic framework material MIL-101(Cr), then heat and stir to react, filter, wash with water and vacuum dry to obtain the metal-organic framework material MIL-101(Cr)-EDTA carrier modified by ethylenediaminetetraacetic acid. The mass ratio of the disodium ethylenediaminetetraacetate dihydrate to the metal-organic framework material MIL-101(Cr) is 0.1 / 1 to 30 / 1; the mass ratio of the disodium ethylenediaminetetraacetate dihydrate to water is 0.02 / 1 to 0.1 / 1.

9. The preparation method according to claim 8, characterized in that: The mass ratio of the disodium ethylenediaminetetraacetate dihydrate to the metal-organic framework material MIL-101(Cr) is 1 / 1 to 10 / 1; the mass ratio of the disodium ethylenediaminetetraacetate dihydrate to water is 0.04 / 1 to 0.06 / 1.

10. The preparation method according to claim 8, characterized in that: The heating reaction temperature is 40~90 ℃, and the duration is 12~36 h. The drying process is vacuum drying, with a vacuum drying temperature of 50~180 ℃ and a drying time of 6~24 h.

11. The preparation method according to claim 10, characterized in that: The heating reaction temperature is 60~80 ℃; the duration is 20~24 h; The drying process is vacuum drying, with a vacuum drying temperature of 80~150 ℃ and a drying time of 10~15 h.

12. The preparation method according to claim 3 or 8, characterized in that: The preparation method of the metal-organic framework material MIL-101(Cr) is as follows: Using chromium ions from chromium salts as metal nodes, terephthalic acid as organic ligands, and acid or base as mineralizing agents, a suspension is formed in water by thorough stirring. The suspension is then transferred to a hydrothermal reactor and subjected to a high-temperature hydrothermal reaction to form a solid. After washing with a hot solvent and drying, the metal-organic framework material MIL-101(Cr) can be obtained. The chromium salt is one or more of chromium nitrate, chromium chloride, chromium sulfate, chromium acetate, and chromium acetylacetone. The reactant ratio is a molar ratio of chromium metal ions to organic ligands ranging from 1 / 10 to 10 / 1, with the concentration of chromium metal ions in water ranging from 0.0001 to 0.0002 mol / L. The mineralizing agent is one or more of the following: hydrofluoric acid, nitric acid, benzoic acid, acetic acid, 2-methylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, sodium acetate, and tetramethylammonium hydroxide; the concentration of nitric acid is 0.21~0.24 mol / L; and the concentration of hydrofluoric acid is 0.12~0.14 mol / L. The hydrothermal reaction temperature is 150~220 ℃, and the hydrothermal duration is 6.0~24 h. The hot solvent is one or more of N,N-dimethylformamide, ethanol, methanol, ammonium fluoride aqueous solution, and chloroform, the heating temperature is 50~80 ℃, and the washing time is 6~20 h.

13. The preparation method according to claim 12, characterized in that: The chromium salt is one or more of chromium nitrate, chromium acetate, and chromium acetylacetone; The reactant ratio is as follows: the molar ratio of chromium metal ions to organic ligands ranges from 0.5 / 1 to 2 / 1; the concentration of chromium metal ions in water is 0.00013 to 0.00018 mol / L. The mineralizing agent is one or two of hydrofluoric acid and nitric acid; The hydrothermal reaction temperature is 200~220 ℃; the hydrothermal duration is 8~10 h; The hot solvent is one or two of N,N-dimethylformamide and ethanol; the heating temperature is 60~80 ℃; and the washing time is 10~15 h.

14. The application of a diatomic catalyst supported on a metal-organic framework material as described in claim 1 or 2 in the catalytic hydrogen esterification of olefins to prepare organic carboxylic acid esters.

15. The application according to claim 14, characterized in that: In the presence of ruthenium supported on ethylenediaminetetraacetic acid-modified metal-organic framework material MIL-101(Cr) and iron / cobalt / nickel bimetallic solid heterogeneous catalyst, alcohols are used as reactants and solvents to prepare organic carboxylic acid esters by hydrogen esterification with olefins and CO under certain temperature and pressure. The reaction temperature is 140~250 ℃, and the reaction pressure is 0.05-20.0 MPa. The raw material olefin is one or more of O1 to O7 in the compound shown in Formula 1; ， The raw material alcohol is one or more of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, benzyl alcohol, and phenylethanol.

16. The application according to claim 15, characterized in that: The reaction temperature is 160~220 ℃; the reaction pressure is 0.5~5 MPa.

17. The application according to any one of claims 14-16, characterized in that: The reaction is carried out in a fixed bed, trickle bed, slurry bed, or batch reactor; when using a fixed bed or trickle bed, the liquid hourly space velocity is 0.01~20.0 h⁻¹. -1 The air space velocity is 100~20000 h. -1 , The molar ratio of ruthenium metal to alcohol in the solid heterogeneous catalyst is 0.00001:1 to 0.001:1, the molar ratio of ruthenium metal to raw olefin in the solid heterogeneous catalyst is 0.0001:1 to 0.05:1, and the molar ratio of ruthenium metal to CO in the solid heterogeneous catalyst is 0.00001:1 to 0.001:

1.

18. The application according to claim 17, characterized in that: When using a fixed bed or trickle bed, the liquid hourly space velocity is 1~5 h⁻¹. -1 The air space velocity is 500~2000 h. -1 ; The molar ratio of ruthenium metal to alcohol in the solid heterogeneous catalyst is 0.00005:1 to 0.0005:1; the molar ratio of ruthenium metal to raw olefin in the solid heterogeneous catalyst is 0.0005:1 to 0.005:1; the molar ratio of ruthenium metal to CO in the solid heterogeneous catalyst is 0.00005:1 to 0.0005:1.

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