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CN113209977A - Preparation method and application of hydrogenation catalyst with tannic acid as stabilizer - Google Patents

Preparation method and application of hydrogenation catalyst with tannic acid as stabilizer Download PDF

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CN113209977A
CN113209977A CN202110364574.7A CN202110364574A CN113209977A CN 113209977 A CN113209977 A CN 113209977A CN 202110364574 A CN202110364574 A CN 202110364574A CN 113209977 A CN113209977 A CN 113209977A
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ceo
cuo
catalyst
hydrogenation
selectivity
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叶俊青
孙剑
冯咪
贺滨
陈欣妍
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a CuO/CeO with Tannic Acid (TA) as a stabilizer2A preparation method of a hydrogenation catalyst and application in p-nitrophenol (4-NP) hydrogenation reaction. The pyrogallol in the tannin can be used for reacting with Cu2+Coordination to form TA-Cu2+And (c) a complex. Then respectively dispersing cerium dioxide carriers with different morphologies in the composite mixed solution, reacting for a certain time, filtering, washing, drying and roasting to obtain the 4-NP hydrogenation catalyst CuO/CeO with high hydrogenation activity and selectivity and capable of being repeatedly used for multiple times2Rods and CuO/CeO2-Cubes. Wherein 0.1 to 10 wt% of CuO/CeO2The dosage of Rods is 0.5-10 mg, and the reaction is carried outUnder the condition that the time is 1-50 minutes, 4-NP with the concentration of 0.05-0.6 mM can be completely catalyzed and hydrogenated to generate a 4-aminophenol (4-AP) product, the conversion rate is 100%, and the selectivity of the 4-AP is 100%. The tannic acid used by the invention is from plants, and has the advantages of greenness, naturalness, no toxicity, harmlessness, low price and the like. Prepared CuO/CeO2The catalyst has low production cost, high hydrogenation activity, good selectivity and good air stability, and can be stored for a long time.

Description

Preparation method and application of hydrogenation catalyst with tannic acid as stabilizer
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a hydrogenation catalyst based on tannic acid and application of the hydrogenation catalyst as a catalyst in hydrogenation reaction.
Background
Para-aminophenol is an important chemical raw material and a medical intermediate, and is widely applied to the fields of medicines, dyes, rubber, pesticides, photosensitive materials and the like. The p-nitrophenol is an organic pollutant and has destructive effect on the environment and the central nervous system of a human body, so that the catalytic conversion of the p-nitrophenol into the p-aminophenol with high added value has important significance and application value.
In recent years, noble metal-based catalysts such as Au, Pt, Pd and the like are widely used as heterogeneous catalytic hydrogenation catalysts, but the heterogeneous catalytic hydrogenation catalysts have the disadvantages of high cost, cluster sintering tendency, low stability and the like. Therefore, it is imperative to find and design non-noble metal catalysts with high activity, low cost and high stability. For example, Cu-based catalysts are attracting more and more researchers' attention due to their low price, abundant earth reserves, and high activity. On the other hand, since CeO2Has good oxygen storage capacity and strong interaction with CuO particles, and the effective synergy and electronic synergy between the active metal and the carrier ensure that the CuO/CeO2The catalyst has high catalytic activity and is widely used for CO oxidation reaction, water gas conversion, hydrocarbon steam reforming and other reactions. In the preparation of CuO/CeO2In the case of heterogeneous catalysts, it is generally necessary to use expensive and toxic Polyethylene (PEG), polyvinylpyrrolidone (PVP), or the like as a stabilizer.
The stabilizer used in the method is tannin derived from plants, and has the advantages of no toxicity, no harm and low cost. The tannin molecule has polyphenol structure characteristics and can react with Cu2+Formation of TA-Cu by chelation2+The complex is further used for preparing CeO with nano CuO particles highly dispersed in different shapes by an impregnation method2CuO/CeO on a support with high stability2The catalyst is applied to the reaction of catalyzing the p-nitrophenol to generate the p-aminophenol with high added value.
Disclosure of Invention
The invention aims to provide a method for preparing a hydrogenation catalyst with high activity and high stability and application of the hydrogenation catalyst in catalyzing p-nitrophenol hydrogenation.
The technical scheme of the invention is as follows:
a preparation method of a hydrogenation catalyst and an application of the hydrogenation catalyst in p-nitrophenol hydrogenation reaction are provided, wherein the hydrogenation catalyst is obtained by the following preparation method:
preparing a Tannic Acid (TA) solution, slowly adding the solution into a prepared metal precursor copper salt (copper nitrate, copper sulfate, copper chloride and the like) solution, magnetically stirring the solution for a period of time at room temperature, and forming TA-Cu through chelation or coordination and the like2+And (c) a complex. Dispersing the prepared cerium dioxide catalyst carriers with different morphologies in deionized water, carrying out ultrasonic treatment for a period of time, and respectively adding the cerium dioxide catalyst carriers into TA-Cu2+The complex mixed solution is stirred for a period of time at room temperature in a beaker to complete the preparation of TA-Cu2+/CeO2A catalyst precursor. Then, the mixture is centrifugally filtered, washed and dried respectively. Finally, roasting for a period of time in a muffle furnace in an air atmosphere to respectively obtain hydrogenation catalysts I (CuO/CeO) with nano CuO particles uniformly distributed on catalyst carriers2Rods) and II (CuO/CeO)2-Cubes). In the hydrogenation catalyst, because abundant ligands exist around the metal center, the metal center has unique electronic state and chemical environment, and the obtained catalyst has excellent catalytic p-nitrophenol hydrogenation performance and stability. In addition, the preparation method has the advantages of cheap and easily obtained raw materials and simple method.
Preferably, the molar ratio of the metal precursor copper salt to the tannic acid is: 0.5-4: 1, and the reaction time is 12-24 hours.
Preferably, the ceria supports with different morphologies are respectively: rod-like and cubic, respectively designated as CeO2Rods (I) and CeO2-Cubes(II)。
Preferably, the ultrasound time is: 0.5 to 1 hour.
Preferably, the drying temperature is: 60-80 ℃.
Preferably, the calcination temperature is: 300-500 ℃; the heating rate in the roasting process is as follows: 1-10 ℃/min; the roasting time is as follows: 3-4 hours.
Preferably, in the hydrogenation catalyst, the mass fraction of copper is 0.1 wt% to 10 wt%.
Preferably, the hydrogenation catalyst is stored for 6 months or more at sealed room temperature.
Preferably, the catalytic p-nitrophenol hydrogenation reaction conditions are as follows: the concentration of the p-nitrophenol is 0.05-0.6 mM; the molar ratio of the sodium borohydride to the p-nitrophenol is 500-150: 1; the dosage of the hydrogenation catalyst is 0.5-10 mg; the temperature is 25-60 ℃; the reaction time is 1-100 minutes.
Compared with the prior art, the invention has the following beneficial effects:
the stabilizer tannic acid required by the synthesis of the catalyst is derived from plants, is green and natural, is nontoxic and harmless, and has low price. The preparation method is simple and easy for large-scale production. Most importantly, the active nano CuO particles in the hydrogenation catalyst synthesized by the method are highly and uniformly dispersed in CeO2Rods and CeO2The catalyst has excellent activity and selectivity in a plurality of specific selective catalytic hydrogenation reactions due to high metal utilization rate on the Cubes carrier.
Detailed Description
The details contained in the following examples are intended to further illustrate the technical solution of the present invention, but are not limited thereto.
Example 1:
in the first step, 0.868g of cerium nitrate is dissolved in 5mL of deionized water at room temperature, and ultrasonic oscillation is carried out for 10 minutes, then a cerium nitrate solution is slowly added into a 6M potassium hydroxide solution with the volume of 35mL, and magnetic stirring is carried out for 1 hour, so as to obtain a milky white suspension.
And secondly, transferring the milky white suspension from the beaker to a 100mL high-temperature high-pressure hydrothermal reaction kettle, and reacting for 24 hours at 100 ℃. After the reaction is finished, respectively carrying out centrifugal filtration on the mixture, washing the mixture for 5 times by using deionized water, putting the mixture into an oven, and standing the mixture at 60 ℃ overnight in an air atmosphere to obtainTo light yellow powder, namely nano rodlike CeO2-Rods vector.
Step three, 6.3mg of copper nitrate is dissolved in 50mL of deionized water, and the mixture is magnetically stirred for a plurality of minutes until the mixture is dissolved; simultaneously dissolving 28.6mg of TA in 10mL of deionized water, and magnetically stirring for a plurality of minutes until the TA is dissolved; the molar ratio of the two is 1: 2.
Fourthly, slowly dripping the TA aqueous solution into the cupric nitrate aqueous solution, and magnetically stirring for 24 hours at room temperature to obtain TA-Cu2+The complex is mixed with the solution.
The fifth step, 0.25g of prepared CeO is taken2-the rds carrier is dispersed in 15mL deionized water and shaken ultrasonically for 1 hour; then adding it to the TA-Cu of the previous step2+And (3) magnetically stirring the compound mixed solution for 24 hours at room temperature, centrifugally filtering, washing with deionized water for 5 times, putting into an oven, and drying at 60-80 ℃.
Sixthly, putting the mixture into a muffle furnace, roasting for 4 hours at the temperature rise rate of 5 ℃/min and the temperature of 400 ℃ in the air atmosphere to obtain CuO/CeO2-Rods catalyst.
Seventhly, taking 2mL of 0.14mM p-nitrophenol aqueous solution, putting the aqueous solution into a cuvette with the width of 1cm, and adding 2mg of NaBH40.8mL of deionized water, 1mg of catalyst, the catalytic hydrogenation reaction started. And detecting the contents of the reactants and the products by using an ultraviolet-visible spectrophotometer UV-Vis, wherein the wavelength range is 250-500 nm. CuO/CeO prepared by using natural non-toxic tannin with plant polyphenol structure as chelating agent and stabilizer2The catalyst shows higher catalytic activity in the catalytic hydrogenation reaction of p-nitrophenol (4-NP). Wherein 1mg of CuO/CeO2-Rods can completely catalyze and hydrogenate 0.1mM 4-NP to generate a 4-aminophenol (4-AP) product in about 5 minutes, the conversion rate is 100 percent, the selectivity of the 4-AP is 100 percent, the catalyst can be repeatedly used for at least 5 times, and no obvious inactivation phenomenon exists.
Example 2:
the difference from the example 1 is that the temperature of the high-temperature high-pressure hydrothermal reaction kettle is 180 ℃, and the white yellow powder which is the nano cubic CeO is obtained2-cube vectors.
Example 3:
the same as example 1 except that 1mg of CuO/CeO was used2The-cube can completely catalyze and hydrogenate 0.1mM 4-NP to generate a 4-aminophenol (4-AP) product in about 11 minutes, the conversion rate is 100%, the selectivity of the 4-AP is 100%, and the product can be repeatedly used for at least 5 times without obvious inactivation.
Example 4:
the same as example 1 except that 1mg of CuO/CeO was used2Rods is capable of completely degrading a 0.1mM Congo Red solution to CO in about 0.5 minute2And H2O, the conversion rate is 100%, and the catalyst can be repeatedly used for at least 10 times without obvious inactivation.
Example 5:
the same as example 1 except that 1mg of CuO/CeO was used2Rods can completely degrade 0.4mM rhodamine B solution to CO in about 2 minutes2And H2O, the conversion rate is 100%, and the catalyst can be repeatedly used for at least 10 times without obvious inactivation.
Example 6:
the same as example 1 except that 1mg of CuO/CeO was used2And Rods can completely catalyze and hydrogenate 0.1mM m-nitrophenol solution in about 1 minute to generate the product m-aminophenol, the conversion rate is 100%, the selectivity of m-aminophenol is 100%, and the product can be repeatedly used for at least 5 times without obvious inactivation.
Example 7:
the method is the same as example 1, except that the molar ratio of copper nitrate to tannic acid is 0.5-4: 1.
Example 8:
the same as example 1 except that the mass of copper nitrate was 3.2 mg. Obtaining CuO/CeO with the mass fraction of 0.1 wt%2-Rods catalyst.
Example 9:
the same as example 1 except that the mass of copper nitrate was 12.6 mg. Obtaining CuO/CeO with the mass fraction of 0.3 wt%2-Rods catalyst.
Example 10:
the difference from example 1 is that of copper nitrateThe mass was 320 mg. Obtaining CuO/CeO with the mass fraction of 10 wt%2-Rods catalyst.
Example 11:
the same as example 1, except that copper nitrate was changed to CuSO4、CuCl2、HAuCl4。
Example 12:
the same as example 1, except that the calcination temperature was 300 ℃ and the temperature increase rate was 5 ℃/min, calcination was carried out for 4 hours.
Example 13:
the same as example 1, except that the calcination temperature was 500 ℃ and the temperature increase rate was 5 ℃/min, calcination was carried out for 4 hours.
Example 14:
the same as example 1, except that the calcination temperature was 400 ℃ and the temperature increase rate was 1 ℃/min, calcination was carried out for 4 hours.
Example 15:
the same as example 1, except that the calcination temperature was 400 ℃ and the temperature increase rate was 10 ℃/min, calcination was carried out for 4 hours.
Example 16:
the same as example 1, except that the calcination temperature was 400 ℃ and the temperature increase rate was 5 ℃/min, calcination was carried out for 3 hours.
Example 17:
the difference from example 1 is that the hydrogenation catalyst is stored for 3 months at sealed room temperature, the conversion rate of 4-NP is 100%, the selectivity of 4-AP is 100%, and the hydrogenation catalyst can be reused for at least 10 times without obvious deactivation.
Example 18:
the difference from example 1 is that the hydrogenation catalyst can be stored for 4 months at sealed room temperature, the conversion rate of 4-NP is 100%, the selectivity of 4-AP is 100%, and the hydrogenation catalyst can be reused for at least 5 times without obvious deactivation.
Example 19:
the difference from example 1 is that the hydrogenation catalyst can be stored for 6 months at sealed room temperature, the conversion rate of 4-NP is 100%, the selectivity of 4-AP is 100%, and the hydrogenation catalyst can be reused for at least 5 times without obvious deactivation.
Example 20:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.05 mM.
Example 21:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.2 mM.
Example 22:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.3 mM.
Example 23:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.4 mM.
Example 24:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.5 mM.
Example 25:
the same as in example 1, except that the initial concentration of p-nitrophenol was 0.6 mM.
Example 26:
the difference from example 1 is that NaBH4The molar ratio to 4-NP was 500:1, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 3 minutes.
Example 27:
the difference from example 1 is that NaBH4The molar ratio to 4-NP was 250:1, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 4 minutes.
Example 28:
the difference from example 1 is that NaBH4The molar ratio to 4-NP was 150:1, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 5 minutes.
Example 29:
the same as example 1, except that the catalyst was added in an amount of 0.5mg to catalyze the hydrogenation of p-nitrophenol, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 10 minutes.
Example 30:
the same as example 1, except that the catalyst was added in an amount of 3mg to catalyze the hydrogenation of p-nitrophenol, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 2 minutes.
Example 31:
the same as example 1, except that the catalyst was added in an amount of 5mg to catalyze the hydrogenation of p-nitrophenol, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was 1 minute.
Example 32:
the same as example 1, except that the catalyst was added in an amount of 10mg to catalyze the hydrogenation of p-nitrophenol, the conversion of 4-NP was 100%, the selectivity of 4-AP was 100%, and the time taken for complete conversion was less than 1 minute.
The invention is not the best known technology.

Claims (6)

1.一种通过单宁酸铜配位负载在不同形貌CeO2载体上的加氢催化剂制备方法，以及该催化剂在对硝基苯酚加氢反应中的应用，其特征在于：将铜盐加入去离子水中，完全溶解得到铜盐水溶液，将单宁酸加入去离子水完全溶解得到单宁酸水溶液，金属前驱体铜盐与单宁酸的摩尔比为：0.5～4:1，磁力搅拌时间为12～24小时，得到TA-Cu2+复合物混合液；然后分别取一定量制备好的CeO2-Rods和CeO2-Cubes载体分散到去离子水中，超声振荡0.5～1小时；然后分别将其加入TA-Cu2+复合物混合液中，室温下，磁力搅拌24小时，离心过滤，洗涤，干燥(温度为60～80℃)；分别将其放入马弗炉中，空气气氛下，升温速率为1～10℃/min，温度为300～500℃，焙烧3～4小时，分别得到CuO/CeO2-Rods和CuO/CeO2-Cubes催化剂。将其应用在催化对硝基苯酚(4-NP)的加氢反应中，其特征在于，一定温度下，在比色皿中加入一定量的4-NP溶液，一定量的NaBH4，一定量的催化剂，反应一段时间，得到产物对氨基苯酚(4-AP)，4-NP的转化率为100％，4-AP的选择性为100％。1. a kind of hydrogenation catalyst preparation method that is supported on different morphology CeO by tannic acid copper coordination support, and the application of this catalyzer in the hydrogenation reaction of p-nitrophenol, it is characterized in that: copper salt is added In deionized water, completely dissolve to obtain copper salt aqueous solution, add tannic acid into deionized water to completely dissolve to obtain tannic acid aqueous solution, the molar ratio of metal precursor copper salt to tannic acid is: 0.5～4:1, magnetic stirring time for 12 to 24 hours to obtain a TA-Cu 2+ complex mixture; then take a certain amount of prepared CeO 2 -Rods and CeO 2 -Cubes carriers and disperse them in deionized water, and ultrasonically shake for 0.5 to 1 hour; Add it to the TA-Cu 2+ complex mixture, stir magnetically for 24 hours at room temperature, centrifugally filter, wash, and dry (temperature is 60-80°C); put it into a muffle furnace respectively, under an air atmosphere , the heating rate is 1-10°C/min, the temperature is 300-500°C, and the calcination is performed for 3-4 hours to obtain CuO/CeO 2 -Rods and CuO/CeO 2 -Cubes catalysts respectively. It is applied in the hydrogenation reaction of catalyzing p-nitrophenol (4-NP), and it is characterized in that, at a certain temperature, a certain amount of 4-NP solution, a certain amount of NaBH 4 , a certain amount of NaBH 4 are added to the cuvette at a certain temperature. The catalyst is reacted for a period of time to obtain the product p-aminophenol (4-AP), the conversion rate of 4-NP is 100%, and the selectivity of 4-AP is 100%. 2.根据权利要求1所述的加氢催化剂的应用，其特征在于：在25～60℃温度下，将1～2mL浓度为0.05～0.6mM的4-NP，NaBH4与4-NP的摩尔比为500～150:1，加入0.5～10mg 0.1～10wt％的CuO/CeO2-Rods催化剂至宽度为1cm的比色皿中，进行催化加氢反应，反应时间为1～50分钟，4-NP的转化率为100％，4-AP的选择性为100％。2. the application of hydrogenation catalyst according to claim 1 is characterized in that: at 25～60 ℃ of temperature, 1～2mL concentration is the 4-NP of 0.05～0.6mM, NaBH 4 and the mole of 4-NP The ratio is 500～150:1, add 0.5～10mg 0.1～10wt% CuO/CeO 2 -Rods catalyst to the cuvette with a width of 1cm, carry out catalytic hydrogenation reaction, the reaction time is 1～50 minutes, 4- The conversion of NP was 100% and the selectivity of 4-AP was 100%. 3.根据权利要求2所述的应用，其特性在于：所使用的催化剂为0.1～10wt％的CuO/CeO2-Cubes，用量为0.5～10mg，反应时间为5～100分钟，4-NP的转化率为100％，4-AP的选择性为100％。3. The application according to claim 2, characterized in that the catalyst used is 0.1-10wt% CuO/CeO 2 -Cubes, the dosage is 0.5-10mg, the reaction time is 5-100 minutes, and the 4-NP The conversion was 100% and the selectivity to 4-AP was 100%. 4.根据权利要求2所述的应用，其特征在于：0.1mM刚果红溶液完全催化降解为CO2和H2O，刚果红的转化率为100％。4 . The application according to claim 2 , wherein the 0.1 mM Congo red solution is completely catalytically degraded into CO 2 and H 2 O, and the conversion rate of Congo red is 100%. 5 . 5.根据权利要求2所述的应用，其特征在于：0.1mM间硝基苯酚溶液完全催化加氢生成产物间氨基苯酚，转化率为100％，选择性为100％。5. The application according to claim 2, wherein the 0.1 mM m-nitrophenol solution is completely catalytically hydrogenated to generate the product m-aminophenol, the conversion rate is 100%, and the selectivity is 100%. 6.根据权利要求1所述的加氢催化剂制备方法，其特征在于金属前驱体为HAuCl4，TA与HAuCl4的摩尔比为1:1，通过单宁酸与金属之间的螯合及配位作用，得到活性金属高度分散在催化剂载体CeO2上的加氢催化剂Au/CeO2-Rods和Au/CeO2-Cubes。6. hydrogenation catalyst preparation method according to claim 1 is characterized in that metal precursor is HAuCl 4 , and the mol ratio of TA and HAuCl 4 is 1:1, by chelating and matching between tannic acid and metal The hydrogenation catalysts Au/CeO 2 -Rods and Au/CeO 2 -Cubes in which the active metals are highly dispersed on the catalyst carrier CeO 2 were obtained.
CN202110364574.7A 2021-04-02 2021-04-02 Preparation method and application of hydrogenation catalyst with tannic acid as stabilizer Pending CN113209977A (en)

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CN115532315A (en) * 2022-09-30 2022-12-30 南京工业大学 Preparation method and application of catalyst for synthesizing low-carbon alcohol by carbon dioxide hydrogenation
CN115606606A (en) * 2022-10-08 2023-01-17 河海大学 Novel metal polyphenol network-loaded metal oxide antibacterial nanoparticles, preparation method and application
CN116726928A (en) * 2023-05-11 2023-09-12 润泰化学（泰兴）有限公司 Co/TiO 2 /Al 2 O 3 Preparation method of catalyst and application of catalyst in preparation of isooctyl alcohol by condensation hydrogenation of n-butyraldehyde

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