CN113546616B - Carbohydrate and biomass derived functionalized carbon dot-metal hybrid catalytic material and application thereof - Google Patents
Carbohydrate and biomass derived functionalized carbon dot-metal hybrid catalytic material and application thereof Download PDFInfo
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Abstract
The invention relates to the field of synthesis of carbohydrate and biomass derived functionalized carbon dot-metal hybrid catalytic materials, and discloses a preparation method of a phosphoric acid carbamic acid functionalized carbon dot-zirconium and aluminum derived from carbohydrate and a preparation method of a biomass derived hydroxyl functionalized carbon dot-zirconium hybrid catalytic material and a value-added conversion method for catalyzing a bio-based platform compound. The preparation method of the hybrid catalytic material has the advantages of wide sources of raw materials of carbohydrate and wood fiber biomass and metal zirconium and aluminum chloride, simple two-step conversion process, low cost and easy industrial amplification. The prepared zirconium-based hybrid material has the advantages of high catalytic efficiency, good reusability, excellent target product yield and the like in the reactions of catalyzing furfural to transfer and hydrogenate for synthesizing furfuryl alcohol, catalyzing levulinic acid, and catalyzing levulinic acid ester to transfer and hydrogenate for synthesizing gamma-valerolactone, and in the reactions of catalyzing furfuryl alcohol to alcoholyze into levulinic acid ester. And the aluminum-based and zirconium-based hybrid materials can be combined for furfuryl alcohol alcoholysis and transfer hydrogenation one-pot synthesis of gamma-valerolactone, so that an excellent target product is provided.
Description
Technical Field
The invention relates to the field of synthesis of organic-metal hybrid materials, in particular to preparation of carbohydrate and biomass derived functionalized carbon dot-metal hybrid catalytic materials and a method for catalyzing value-added conversion of bio-based platform compounds by using the hybrid catalytic materials.
Background
Lignocellulosic biomass is the most abundant renewable resource in nature, and the development of value-added utilization or conversion technology thereof is one of the important ways to solve the current fossil resource and energy crisis. The preparation of solid acid catalysts or acidic ligands by using lignocellulosic biomass is considered to be a value-added conversion method with the highest performance price, and the value-added conversion method is used for converting the solid acid catalysts or acidic ligands into various bio-based platform chemicals such as furfural, furfuryl alcohol, levulinic acid, levulinate ester and gamma-valerolactone, so that abundant chemical raw materials and intermediates can be provided for the chemical industry, the food industry and the pharmaceutical industry. Although these platform compounds can be obtained by consecutive conversion reactions of carbohydrates such as cellulose, hemicellulose, disaccharides, monosaccharides, etc., the synthesis of the platform compounds directly from these carbohydrates has the disadvantages of many side reactions, easy inactivation of catalyst, poor product selectivity, low yield, difficult purification, etc. due to the rigor and complexity of the consecutive conversion reaction conditions. Therefore, the development of a high-efficiency value-added transformation method based on the biomass-derived platform compound is more practical.
Generally, the methods for preparing biochar-based solid acid are general methods for preparing the biochar-based solid acid by carbonizing lignocellulosic biomass, sulfonating by concentrated or fuming sulfuric acid, activating and carbonizing by concentrated phosphoric acid and the like, but the solid acid containing only B acid sites has single catalytic function and poor structure and acid site stability, and is difficult to be applied to acid catalytic conversion, particularly value-added conversion reaction of acid catalytic carbohydrate on a large scale. Therefore, new structure and function enhancement strategies need to be developed to prepare biomass carbon-based catalysts for efficient value-added conversion reactions of bio-based platform compounds.
Among bio-based platform compounds, furfural is readily available in high yields from the acid-catalyzed hydrolysis of rice bran or a large amount of hemicellulose by-produced in the paper industry [ Front Chem, 6 (2018) 146]. Many platform compounds with wide application can be synthesized based on the furfural value-added transformation chain, so that the furfural value-added transformation chain is one of the most important biorefinery technologies. A valuable value-added conversion chain comprises catalytic hydrogenation reduction of furfural into furfuryl alcohol, catalytic alcoholysis of furfuryl alcohol into levulinic acid ester, and catalytic hydrogenation of levulinic acid ester into gamma-valerolactone, and the three value-added conversions all have excellent target product yields. Wherein the addition of furfuralThe hydrogenation reaction can use molecular hydrogen or secondary alcohol as hydrogen donor; the catalytic transfer hydrogenation of levulinic acid and levulinate ester can use molecular hydrogen, molecular hydrogen generated by formic acid decomposition or secondary alcohol as hydrogen donor [ Renewable able stable Energy Rev., 2014, 40, 608-620]. The use of molecular hydrogen has the problems of unsafety and the like caused by storage and transportation, the use of noble metal catalysts and high reaction operating pressure; the hydrogen production by using formic acid and the subsequent hydrogenation also have the problems of use of noble metal catalysts, higher decomposition temperature, safety brought by obvious pressure rise of a reaction system and the like; meerwein-Ponndorf-Verley type catalytic conversion hydrogenation (CTH) based on secondary alcohol as a hydrogen donor is widely applied to CTH reaction of furfuryl alcohol, levulinic acid and levulinic acid due to high reaction operation safety and the fact that a low-cost transition metal catalyst can be used. Many catalysts can be applied to the CTH conversion reaction, among which a zirconium-based catalyst has been widely studied with relatively inexpensive and mild reaction conditions, and excellent CTH activity and stability. Zr (OH) 4 、ZrO 2 , ZrCl 4 、Zr(SO 4 ) 2 And Zr 3 (PO 4 ) 4 The zirconium compounds have the cost advantage of being cheap and easy to obtain as CTH catalysts, but the CTH activity and stability of the zirconium compounds are still to be improved. The hybrid material formed by coordination assembly of organic acids such as cyanuric acid and terephthalic acid, biomacromolecule acids such as phytic acid and lignosulfonic acid and zirconium compounds can significantly improve the CTH activity and stability of zirconium, wherein zirconium phytate (Zr-PhA) reported by Song et al is the most excellent CTH catalyst, and 99.3% of furfuryl alcohol and 96.7% of gamma-valerolactone yield are respectively provided in the CTH reaction of furfural and levulinic acid [ Angew. Chem. Int. Edit.54 (2015) 9399-9403]. However, the widespread use of Zr-PhA in CTH reactions is still limited by the high cost of phytic acid. In the reaction of converting furfuryl alcohol into levulinate through alcoholysis, various inorganic liquid B or L acids as the cheapest homogeneous catalyst show better catalytic activity, wherein AlCl 3 As a strong L acid catalyst, the catalyst shows excellent catalytic activity in the reaction of catalyzing the alcoholysis of furfuryl alcohol to be converted into n-butyl levulinate in an n-butyl alcohol medium, and the yield of a target product is as high as 95.7% [ Fuel, 160 (2015) 123-131]. However, the widespread use of these inorganic liquid acids, including solid inorganic acids, still leaves a waste acid reservoirProblems of complex separation and purification of products, equipment corrosion, environmental pollution and the like; sulfonic acid resin, mesoporous silicon-aluminum molecular sieve and SO 4 2- /TiO 2 Sulfonic acid functionalized ionic liquid and graft type heteropoly acid as a recyclable solid acid catalyst and also shows excellent catalytic activity and stability in heterogeneous catalysis of alcoholysis reaction, wherein the sulfonic acid functionalized molecular sieve SBA-15-SO 3 H is taken as a representative strong B acid catalyst, the catalyst shows excellent catalytic activity in the reaction of catalyzing furfuryl alcohol alcoholysis to be converted into ethyl levulinate in an ethanol medium, and the yield of the target product ethyl levulinate reaches 96% [ ChemSusChem, 7 (2014) 835-840%]. However, the large-scale application of these solid acids is still limited by the disadvantages of complicated preparation, high cost, single acid site, low catalytic alcoholysis efficiency, etc. of most of them. In addition, the presently reported alcoholysis catalyst has low catalytic efficiency (the target product yield is 66-92%) in the reaction of catalyzing the alcoholysis of furfuryl alcohol into isopropyl acetoacetate in an isopropanol medium, and the catalyst and a zirconium-based catalyst are combined to be applied to a one-pot conversion reaction of co-catalyzing the alcoholysis of furfuryl alcohol in the isopropanol medium and synthesizing gamma-valerolactone by transfer hydrogenation.
In conclusion, the development of B-L double-acid type catalysts which have low raw material cost and simple preparation and can be used for efficiently catalyzing the transfer hydrogenation and alcoholysis reactions in the furfural value-added conversion chain is urgent. The invention provides a preparation method of series organic-inorganic hybrid catalytic materials PCQD-Zr, PCQD-Al and BCQD-Zr which are assembled by coordination of carbohydrate and biomass derived functionalized carbon points and zirconium and aluminum compounds based on the above purpose, and the preparation method has the advantages of cheap and easily obtained raw materials, simple and convenient operation steps, low cost and easy amplification production. The yield of 98.4 percent furfuryl alcohol can be provided by catalyzing furfural CTH reaction by BCQD-Zr in isopropanol medium; the yield of 97.7 percent isopropyl acetopropionate can be provided by catalyzing furfuryl alcohol alcoholysis reaction by PCQD-Al in an isopropanol medium; PCQD-Zr can provide 98 percent of gamma-valerolactone yield in the CTH reaction of catalyzing levulinic acid or levulinic acid ester in isopropanol medium; the mixed catalyst of PCQD-Al and PCQD-Zr can provide 88.8 percent of gamma-valerolactone yield in the one-pot conversion reaction of catalyzing the alcoholysis of furfuryl alcohol in an isopropanol medium and the transfer hydrogenation.
Disclosure of Invention
The invention aims to provide a method for preparing carbohydrate and biomass derived functionalized carbon dot-zirconium and aluminum series organic-inorganic hybrid catalytic materials PCQD-Zr, PCQD-Al and BCQD-Zr in a large scale at low cost by using lignocellulose biomass, carbohydrate and zirconium and aluminum chloride as main raw materials through simple two-step conversion, and a method for performing value-added conversion on furfural into furfuryl alcohol, levulinate and gamma-valerolactone by using the hybrid high-efficiency catalyst. The preparation method of the PCQD-Zr, the PCQD-Al and the BCQD-Zr has the advantages of cheap and easily obtained raw materials, simple operation, easy amplification, stronger L acid and B acid positions, less catalyst consumption, high catalysis efficiency, good stability, excellent target product yield and the like in the catalysis of furfural value-added conversion reaction. Solves the problems that most of high-efficiency catalysts used in the existing furfural value-added conversion reaction system generally have complex synthesis route, high production cost, low catalytic efficiency, easy inactivation during high-concentration low-product conversion and the like.
The invention provides a preparation method of a carbohydrate and biomass derived functionalized carbon dot-metal hybrid catalytic material, which is characterized by comprising the following steps:
(1) Carrying out heat treatment on carbohydrate by concentrated phosphoric acid and urea to obtain phosphoric acid and carbamic acid functionalized carbon-point PCQD aqueous solution; carrying out hydro-thermal treatment on biomass by using a sodium hydroxide solution to obtain a hydroxyl-functionalized biomass carbon dot BCQD solution;
(2) Mixing the PCQD aqueous solution obtained in the step (1) with ZrCl 4 Or AlCl 3 Mixing the aqueous solutions; aqueous BCQD solution and ZrCl 4 Mixing the aqueous solutions; and then carrying out hydrothermal treatment on the mixed solution at a certain temperature and pH value for 12h to obtain a series of hybrid catalytic materials PCQD-Zr, PCQD-Al and BCQD-Zr.
The invention also provides a method for efficiently catalyzing furfural value-added conversion by using the hybrid materials. Under the action of a hybrid catalyst, transferring and hydrogenating furfural to furfuryl alcohol, performing alcoholysis of furfuryl alcohol to levulinic acid ester, and transferring and hydrogenating levulinic acid ester to gamma-valerolactone, wherein the catalysts for the transfer hydrogenation reaction of furfural and levulinic acid ester are respectively BCQD-Zr and PCQD-Zr of the invention, and the catalyst for the alcoholysis reaction of furfuryl alcohol is PCQD-Al of the invention; the method also comprises the step of synthesizing gamma-valerolactone by furfuryl alcohol through alcoholysis and transfer hydrogenation one-pot method under the action of a hybrid catalyst, wherein the hybrid catalyst is a mixture of PCQD-Al and PCQD-Zr; the method also comprises the transfer hydrogenation of levulinic acid into gamma valerolactone under the action of the hybrid catalyst, wherein the hybrid catalyst is the PCQD-Zr disclosed by the invention.
Compared with the prior art, the invention has the following outstanding advantages:
1) The carbohydrate and biomass derived functionalized carbon dot-zirconium and aluminum series organic-inorganic hybrid catalytic materials PCQD-Zr, PCQD-Al and BCQD-Zr prepared by the method have the outstanding advantages of cheap and easily obtained raw materials, short preparation flow, low cost, high efficiency, stronger double acid sites of L and B, good stability and the like;
2) The prepared BCQD-Zr and PCQD-Zr respectively catalyze CTH reaction of furfural and levulinic acid or levulinate ester in an isopropanol medium and catalyze furfuryl alcohol alcoholysis reaction of the prepared PCQD-Al in the isopropanol medium, and have the outstanding advantages of high used substrate concentration, small catalyst dosage, high catalytic efficiency, excellent target product yield and good reusability.
Detailed Description
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention.
Example 1
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr by using bamboo powder as a raw material specifically comprises the following steps:
(1) Weighing 6.0 g bamboo powder, dispersing the bamboo powder in 50 mL of NaOH solution (the amount of NaOH is 60 to 100wt% of the mass of the bamboo powder), and stirring at room temperature for several hours; and then transferring the mixture into a 100mL hydrothermal crystallization kettle with a polytetrafluoroethylene lining, and placing the hydrothermal crystallization kettle in a constant-temperature oven at 180-200 ℃ for heat preservation for 9-12 h. And finally, after the kettle is naturally cooled, centrifuging the mixture, removing a small amount of sediment (about 0.2 to 0.1g) at the bottom, and collecting the deep red brown alkaline aqueous solution of the hydroxyl functionalized Biomass Carbon Quantum Dots (BCQD).
(2) The aqueous alkaline BCQD solution 10 mL (about 1.0g BCQD) prepared above and 1.5g ZrCl were taken 4 (the dosage is 1.5 times of the dosage of BCQD by mass) is dissolved in 45 mL water to obtain a zirconium sol solution, and the zirconium sol solution is simultaneously dripped into 15 mL hydrochloric acid solution with the pH value of 2, the pH value of the solution is kept unchanged, and after the dripping is finished, the solution is stirred for a plurality of hours at room temperature. The mixture was then transferred to a 100mL hydrothermal crystallization kettle with a teflon liner, and held in a constant temperature oven at 120 ℃ for 12h. After the kettle is naturally cooled, the mixed solution is filtered, washed by deionized water, leached and precipitated until no Cl exists in the filtrate - And drying the obtained solid at 60 ℃ for one night under a vacuum condition to obtain the target catalyst BCQD-Zr-1.
Example 2
The method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-zirconium hybrid catalyst PCQD-Zr-1 by using glucose as a raw material specifically comprises the following steps:
(1) Accurately weighing 5.0 zxft 3425 glucose, 6.39 g concentrated phosphoric acid (mass fraction is 85%) and 10.0 g urea (the molar ratio of the three raw materials is respectively 1. The product was finally collected, washed with 80% (v/v) aqueous methanol (20 mL x 3) and methanol (20 mL x 1) and dried in a vacuum oven at 60 ℃ for 12h to give glucose grafted with phosphate groups, carbamate, labeled PCQD-Gu-1.
(2) Under ultrasonic wave, 0.5 g of PCQD-1 and 0.75g of ZrCl 4 (the dosage is 1.5 times of that of PCQD-1 by mass) are respectively dissolved in 8mL and 10 mL deionized water to obtain the products based on PCQD-1 and ZrCl 4 Derivatized sol solution. Subsequently, the two sol solutions were mixed and stirred at room temperature with a magnetic stirrer for 30 min during which a brown solid was presentThe body gradually precipitated out of the reaction solution. The resulting mixture was then transferred to a 25 mL teflon lined reactor which was sealed and placed in an oven preheated to 120 ℃. And carrying out hydrothermal treatment on 12h in an oven under the autogenous pressure of 120 ℃, taking out the stainless steel reaction kettle, and cooling to room temperature. Filtration gave a brown precipitate which was washed with distilled water and absolute ethanol (10 mL × 3) until the filtrate became colorless and Cl-free - And neutral (pH = 7). And drying the obtained brown precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain the target product, namely, the phosphoric acid carbamate glucose carbon-point-zirconium hybrid material (marked as PCQD-Zr-Gu-1).
The zirconium contents of BCQD-Zr-1 and PCQD-Zr-Gu-1 are respectively determined by ICP analysis and high-temperature combustion method, the zirconium contents of BCQD-Zr-1 and PCQD-Zr-Gu-1 are 36.4 Wt% and 53.0 Wt% by mass through ICP analysis, and the zirconium contents of the two catalysts are 36.9 Wt% and 53.4Wt% by mass through high-temperature combustion method, and the zirconium contents are basically equivalent. Therefore, the subsequent measurement of the zirconium content of the BCQD-Zr and phosphoric acid carbamic acid functionalized carbon dot-zirconium hybrid material series samples adopts a high-temperature combustion method. BET, XRD and SEM characterization results show that BCQD-Zr-1 is a non-porous amorphous network structure material; the PCQD-Zr-Gu-1 is a porous and amorphous net structure material, and the BET surface area, the pore volume and the average pore diameter of the material are respectively 224 m 2 .g -1 , 0.4 cm 3 .g -1 And 10.9 nm; the pyridine adsorption infrared spectroscopy characterization proves that the BCQD-Zr-1 mainly contains zirconium ion derived L acid sites and few phenolic hydroxyl group derived weak B acid sites, and the PCQD-Zr-Gu-1 contains zirconium ion derived L acid sites and phosphoric acid derived medium strong B acid sites.
Comparative example 1: zrO prepared by the comparative example 2 The hydrothermal preparation method comprises the following steps:
(1) 1.5g ZrCl was weighed 4 Dissolving in 20 mL deionized water to obtain sol;
(2) Then the obtained sol is transferred to a 25 mL reaction kettle with a polytetrafluoroethylene lining for sealing, and the reaction kettle is placed into an oven preheated to 120 ℃. And carrying out hydrothermal treatment on 12h in an oven under the autogenous pressure of 120 ℃, taking out the stainless steel reaction kettle, and cooling to room temperature. FiltrationA white precipitate was obtained, which was washed with distilled water (10 mL X3) until the filtrate became colorless and free of Cl - And neutral (pH = 7). Drying the obtained white precipitate in a vacuum drying oven at 60 ℃ for 12h to obtain a target product ZrO 2 。
Experimental example 1 (1-1~1-3): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating furfural (FF) in isopropanol through high-efficiency catalysis in the test example specifically comprises the following steps: a10 ml hydrothermal crystallization kettle (polytetrafluoroethylene lining and stainless steel jacket) is used as a reactor. 1 mmol of furfural (FF), 0.1g of BCQD-Zr-1 synthesized in example 1, PCQD-Zr-Gu-1 synthesized in example 2, and ZrO synthesized in comparative example 1, respectively, were taken 2 The catalyst, 4 ml isopropanol, was added to the liner. Placing the mixture into an oil bath kettle which is heated to 100 ℃ to be stirred and reacted for 2 to 3 hours. After the reaction, the reactor was placed in a flowing cold air stream to be cooled to room temperature, the reaction solution was filtered using a 5 ml syringe and a 0.22 μm organic frit, and the filtered reaction solution was injected into a vial for vapor phase detection, and the product yield was calculated by the internal standard method using n-dodecane as an internal standard substance. The reaction results are shown in Table 1.
TABLE 1
As can be seen from Table 1, although the Zr content of BCQD-Zr-1 is the lowest, it is the most excellent catalyst for Catalytic Transfer Hydrogenation (CTH) of furfural, and the yield of furfuryl alcohol, which is the target product, is as high as 98.4%.
Example 3 (3-1~3-3)
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr by using bamboo powder as a raw material specifically comprises the following steps: the preparation process as described in example 1 is followed, except that ZrCl is changed in operation (2) 4 BCQD-Zr-2, BCQD-Zr-3 and BCQD-Zr-4 were prepared in amounts of 1.0g, 1.25 g and 1.75 g, respectively, which were 1 times, 1.25 times and 1.75 times the amount of BCQD by mass.
Experimental example 2 (2-1~2-3): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating catalytic furfural (FF) in isopropanol specifically comprises the following steps: the evaluation method described in test example 1 was followed except that BCQD-Zr-2, BCQD-Zr-3 or BCQD-Zr-4 prepared by the method described in example 3 was used as the catalyst, and the reaction time was 3h. The reaction results are shown in Table 2.
TABLE 2
As can be seen from Table 2, zrCl was used with the preparation of BCQD-Zr 4 The amount is increased, the Zr content in the catalyst is gradually increased, the CTH activity is increased and then reduced, and ZrCl is used 4 BCQD-Zr-1 prepared in an amount of 1.5 times that of BCQD had the best CTH activity.
Example 4 (4-1~4-2)
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr by using bamboo powder as a raw material specifically comprises the following steps: BCQD-Zr-5 and BCQD-Zr-6 were prepared according to the preparation method described in example 1, except that the pH of the hydrochloric acid solution used was changed to 1 and 3, respectively, in operation (2).
Experimental example 3 (3-1~3-2): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating furfural (FF) in isopropanol through high-efficiency catalysis in the test example specifically comprises the following steps: the evaluation method described in test example 1 was followed, except that BCQD-Zr-5 or BCQD-Zr-6 prepared by the method described in example 4 was used as the catalyst, and the reaction time was 3h. The reaction results are shown in Table 3.
TABLE 3
As can be seen from Table 3, as the pH of the hydrochloric acid solution used for preparing BCQD-Zr increased, the Zr content in the catalyst gradually increased and the CTH activity thereof decreased after increasing, and BCQD-Zr-1 prepared at pH 2 of the hydrochloric acid solution used had the best CTH activity.
Example 5 (5-1~5-3)
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr by using bamboo powder as a raw material specifically comprises the following steps: the preparation process as described in example 1 was followed, except that the hydrothermal treatment temperatures used in operation (2) were changed to 25 deg.C, 60 deg.C and 150 deg.C, respectively, to thereby prepare BCQD-Zr-7, BCQD-Zr-8 and BCQD-Zr-9.
Experimental example 4 (4-1~4-3): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating furfural (FF) in isopropanol through high-efficiency catalysis in the test example specifically comprises the following steps: the evaluation method described in test example 1 was followed, except that the catalyst used was BCQD-Zr-7, BCQD-Zr-8 or BCQD-Zr-9 prepared by the method described in example 5, and the reaction time was 3h. The reaction results are shown in Table 4.
TABLE 4
As can be seen from Table 4, as the hydrothermal treatment temperature used for preparing BCQD-Zr increased, the Zr content in the catalyst gradually increased and reached the maximum at 120 ℃; the CTH activity increased significantly with the treatment temperature, reaching a maximum at a treatment temperature of 120 ℃, but a further increase in the treatment temperature resulted in a significant decrease in the furfuryl alcohol yield.
Example 6 (6-1~6-3)
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr by using bamboo powder as a raw material specifically comprises the following steps: the preparation process as described in example 1 was followed, except that the hydrothermal treatment times used in operation step (2) were changed to 8 hr, 16 hr and 20 hr, respectively, to thereby prepare BCQD-Zr-10, BCQD-Zr-11 and BCQD-Zr-12.
Experimental example 5 (5-1~5-3): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating furfural (FF) in isopropanol through high-efficiency catalysis in the test example specifically comprises the following steps: the evaluation method described in test example 1 was followed, except that BCQD-Zr-10, BCQD-Zr-11 or BCQD-Zr-12 prepared by the method described in example 6 was used as the catalyst, and the reaction time was 3h. The reaction results are shown in Table 5.
TABLE 5
As can be seen from Table 5, as the hydrothermal treatment time for the preparation of BCQD-Zr was increased, the Zr content in the catalyst gradually increased and reached the highest value in 12 h; the furfuryl alcohol yield is increased to 98.0 percent, and the furfuryl alcohol yield is not greatly influenced by further prolonging the time.
Example 7 (7-1~7-3)
The method for preparing the hydroxyl-functionalized carbon dot-zirconium hybrid catalyst BCQD-Zr from other wood fiber biological extraction raw materials in the embodiment specifically comprises the following steps: the preparation process as described in example 13 was followed, except that the biomass used in operation (1) was wood flour, tea leaves and pericarp, respectively, to thereby prepare BCQD-Zr-13, BCQD-Zr-14 and BCQD-Zr-15.
Experimental example 6 (6-1~6-3): the evaluation method for synthesizing Furfuryl Alcohol (FAL) by transferring and hydrogenating high-efficiency catalytic furfural (FF) in isopropanol specifically comprises the following steps: the evaluation method described in test example 1 was followed, except that the catalyst used was BCQD-Zr-13, BCQD-Zr-14 or BCQD-Zr-15 prepared by the method described in example 7, and the reaction time was 3h. The reaction results are shown in Table 6.
TABLE 6
As can be seen from table 6, the biomass used to prepare the hydroxyl functionalized biomass carbon quantum dots had a slight effect on the zirconium content and CTH activity of the synthesized zirconium-based catalyst, with BCQD-Zr-1 prepared using bamboo powder as a raw material having the highest Zr content and the best CTH activity.
Experimental example 7 (7-1~7-10): in this test example, the influence of the reaction conditions on the synthesis of Furfuryl Alcohol (FAL) by transferring and hydrogenating furfural (FF) in isopropyl alcohol (IPA) or sec-butyl alcohol (2-BA) was examined by the evaluation method described in test example 1 using BCQD-Zr-1 as a catalyst. The reaction results are shown in Table 7.
TABLE 7
Test example 8: this test example BCQD-Zr-1 and ZrO were used in accordance with the evaluation method described in test example 1 2 For the catalyst, the reusability of the catalyst in the reaction of catalyzing furfural (FF) to synthesize Furfuryl Alcohol (FAL) by Isopropanol (IPA) transfer hydrogenation is considered, and the reaction time is 3h. The catalyst after each reaction was used directly for the next reaction after centrifugation and washing with IPA, and the results of 5 repeated uses are shown in Table 8.
TABLE 8
| Number of reaction times | Catalyst and process for preparing same | Yield of FAL/% | Number of reaction times | Catalyst and process for preparing same | Yield of FAL/%) |
| 1 | BCQD-Zr-1 | 98.0 | 1 | ZrO 2 | 94.8 |
| 2 | BCQD-Zr-1 | 97.6 | 2 | ZrO 2 | 90.4 |
| 3 | BCQD-Zr-1 | 97.5 | 3 | ZrO 2 | 78.3 |
| 4 | BCQD-Zr-1 | 97.2 | 4 | ZrO 2 | 65.9 |
| 5 | BCQD-Zr-1 | 96 | 5 | ZrO 2 | 65.7 |
As can be seen from Table 8, BCQD-Zr-1 still gave a yield of 96% furfuryl alcohol after the 5 th run, which was only a 2% reduction from the first result; and ZrO 2 Furfuryl alcohol yield after run 5 only65.7% is obtained, which is only a 29% reduction compared to the first result. This indicates that the BCQD-coordinated zirconium-based catalyst has far higher reuse performance than the pure zirconium-based catalyst.
Example 8
The method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-aluminum hybrid catalyst PCQD-Al by using glucose as a raw material specifically comprises the following steps:
(1) The phosphoric acid carbamate functionalized glucose carbon point PCQD-1 is prepared according to the operation step (1) in the example 2;
(2) The procedure was followed as in example 2, except that in the procedure (2), 1.5g of ZrCl was used 4 With 1.356 g AlCl 3 .6H 2 Substitution of O with AlCl 3 .6H 2 The amount of O is 2.7 times of that of the PCQD-1 ligand by mass, and the PCQD-1 and AlCl treated under the same hydrothermal condition 3 .6H 2 The O mixture was cooled, evaporated to dryness at 80 ℃ and dried in an oven at 80 ℃ to 12h. Finally, repeatedly washing the dried sample by using a large amount of absolute ethyl alcohol until the filtrate is neutral and does not contain Cl - And drying the washed sample in a vacuum drying oven at 60 ℃ overnight to obtain the phosphoglucamine carbopoint-aluminum hybrid material (marked as PCQD-Al-1).
Comparative example 2: the method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-aluminum hybrid catalyst PCQD-Al by using glucose as a raw material specifically comprises the following steps: the preparation process as described in example 8 is followed, except that in operation (2) anhydrous AlCl is used 3 Replace AlCl 3 .6H 2 O in an amount of 0.75g, thereby obtaining PCQD-Al (R).
The aluminum contents of PCQD-Al-1 and PCQD-Al (R) were measured by a high temperature combustion method, and the contents of the inorganic aluminum species in the two samples were measured to be 49.2 Wt% and 49.0 Wt% by mass, respectively, which were substantially equivalent to each other. BET, XRD and SEM characterization results show that PCQD-Al-1 is a non-porous and crystal phase structure material; characterization by pyridine adsorption infrared spectroscopy confirms that PCQD-Al-1 mainly contains an aluminum ion-derived L acid site and a phosphoric acid-derived moderately strong B acid site.
Experimental example 9 (9-1~9-5): the evaluation method for synthesizing isopropyl acetoacetate (IPL) by alcoholysis of Furfuryl Alcohol (FAL) in Isopropanol (IPA) by high-efficiency catalysis described in the test example specifically comprises the following steps: a10 mL hydrothermal crystallization kettle (polytetrafluoroethylene lining and stainless steel jacket) is used as a reactor. 1 mmol of furfuryl alcohol (FF), 3.8mL of IPA, 0.1g of PCQD-Al-1 synthesized in example 8, PCQD-Al (R) synthesized in comparative example 2, and commercial AlCl were taken 3 、AlPO 4 Or Al 2 O 3 Catalyst is added to the liner. It was placed in an oil bath pan which had been heated to 120 ℃ and reacted for 10h with stirring. After the reaction, the reactor was placed in a flowing cold air stream to be cooled to room temperature, the reaction solution was filtered using a 5 mL syringe and a 0.22 μm organic frit, and the filtered reaction solution was injected into a vial for vapor phase detection, and the product yield was calculated by the internal standard method using n-dodecane as an internal standard substance. The reaction results are shown in Table 9.
TABLE 9
| Test examples | Aluminum-based catalyst | FAL conversion/% | IPL yield/% |
| 9-1 | PCQD-Al-1 | 100 | 97.7 |
| 9-2 | PCQD-Al (R) | 100 | 97.6 |
| 9-3 | AlCl 3 | 100 | 77.9 |
| 9-4 | AlPO 4 | 0 | 0 |
| 9-5 | Al 2 O 3 | 0 | 0 |
As can be seen from Table 9, the aluminum contents of PCQD-Al-1 and PCQD-Al (R) are equivalent, both of them show excellent catalytic activity in catalyzing the alcoholysis reaction of furfuryl alcohol, and the yield of the target product IPL is as high as 97% or more. AlCl 3 Also shows good alcoholysis activity, but AlPO 4 And Al 2 O 3 No alcoholysis activity.
Example 9 (9-1~9-5)
The method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-aluminum hybrid catalyst PCQD-Al by using glucose as a raw material specifically comprises the following steps: the process as described in example 8 was followed, except that in operation (1) the amounts of concentrated phosphoric acid and urea were varied so that the molar ratios of glucose to concentrated phosphoric acid to urea were 1:1: 4. 1:3: 6. 1:2: 4. 1:2:5 and 1:2: thus, PCQD-Al-2, PCQD-Al-3, PCQD-Al-4, PCQD-Al-5 and PCQD-Al-6 were prepared.
Test examples 10 (10-1 to 10-5): the evaluation method for synthesizing isopropyl acetoacetate (IPL) by alcoholysis of high-efficiency catalytic Furfuryl Alcohol (FAL) in isopropanol described in this test example specifically includes the following steps: the evaluation method described in test example 9 was followed except that the catalyst used was PCQD-Al-2, PCQD-Al-3, PCQD-Al-4, PCQD-Al-5 or PCQD-Al-6 prepared by the method described in example 9. The reaction results are shown in Table 10.
Watch 10
As can be seen from table 10, glucose for the synthesis of the PCQD ligand; phosphoric acid: the molar ratio of the urea has influence on the preparation of the PCQD-Al catalyst, and the PCQD ligand synthesized by using low phosphoric acid and/or urea dosage is not beneficial to preparing an excellent PCQD-Al alcoholysis catalyst and preparing glucose optimized by the PCQD ligand; phosphoric acid: the molar ratio of urea is 1:2:6.
example 10 (10-1 to 10-3)
The method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-aluminum hybrid catalyst PCQD-Al by using glucose as a raw material specifically comprises the following steps: the preparation process as described in example 8 is followed, except that AlCl is changed in operation (2) 3 .6H 2 The amounts of O used were 0.5 g, 1.02 g and 1.695, g, which were 1 time, 2 times and 3.4 times by mass as much as the PCQD-1 ligand, respectively, to thereby prepare PCQD-Al-7, PCQD-Al-8 and PCQD-Al-9.
Test example 11 (11-1 to 11-3): the evaluation method for synthesizing isopropyl acetoacetate (IPL) by alcoholysis of high-efficiency catalytic furfuryl alcohol) FAL) in isopropanol described in the experimental example specifically comprises the following steps: the evaluation method described in test example 9 was followed except that PCQD-Al-7, PCQD-Al-8 or PCQD-Al-9 prepared by the method described in example 10 was used as a catalyst. The reaction results are shown in Table 11.
TABLE 11
| Test examples | Aluminum-based catalyst | AlCl 3 .6H 2 PCQD/Mass ratio | FAL conversion/% | IPL yield/% |
| 11-1 | PCQD-Al-7 | 1.0 | 46.8 | 45.9 |
| 11-2 | PCQD-Al-8 | 2.0 | 78.9 | 76.6 |
| 9-1 | PCQD-Al-1 | 2.7 | 100 | 97.7 |
| 11-3 | PCQD-Al-9 | 3.4 | 100 | 97.2 |
As can be seen from Table 11, the alcoholysis activity of PCQD-Al is dependent on AlCl 3 .6H 2 Increase in mass ratio of O to PCQDThe increase is rapid and reaches the maximum at a mass ratio of 2.7.
Example 11 (11-1 to 11-5)
The method for preparing the phosphoric acid carbamic acid functionalized glucose carbon dot-aluminum hybrid catalyst PCQD-Al by using glucose as a raw material specifically comprises the following steps: the preparation process as described in example 8 was followed, except that no hydrothermal treatment was performed in operation (2), or the hydrothermal treatment temperature was changed to 100 ℃ and 140 ℃, respectively, and the hydrothermal treatment time was changed to 8h and 16h, respectively, to thereby prepare PCQD-Al-10, or PCQD-Al-11 and PCQD-Al-12, and PCQD-Al-13 and PCQD-Al-14.
Test example 12 (12-1 to 12-5): the evaluation method for synthesizing isopropyl levulinate (IPL) by alcoholysis of high efficiency catalytic Furfuryl Alcohol (FAL) in isopropanol in this test example specifically comprises the following steps: the evaluation method described in test example 9 was followed except that PCQD-Al-10, PCQD-Al-11, PCQD-Al-12, PCQD-Al-13 or PCQD-Al-14 prepared by the method described in example 11 was used as a catalyst. The reaction results are shown in Table 12.
TABLE 12
As can be seen from Table 12, the alcoholysis activity of PCQD-Al-10 prepared without hydrothermal treatment is poor, and the alcoholysis activity of PCQD-Al can be generally improved to different degrees by using different hydrothermal treatment temperatures or times, and the optimum hydrothermal treatment temperatures and times are 120 ℃ and 12h respectively.
Example 12 (12-1 to 12-3)
The method for preparing the phosphoric acid carbamic acid functionalized carbon dot-aluminum hybrid catalyst by using other carbohydrates as raw materials in the embodiment specifically comprises the following steps: the preparation process described in example 8 was followed, except that the glucose feedstock was replaced with cellobiose, xylose and fructose, respectively, in operation (1), thereby preparing PCQD-Al-15, PCQD-Al-16 and PCQD-Al-17.
Test example 13 (13-1 to 13-3): the evaluation method for synthesizing isopropyl levulinate (IPL) by alcoholysis of furfuryl alcohol in isopropanol under high efficiency catalysis in this test example specifically comprises the following steps: the evaluation method described in test example 9 was followed except that the catalyst was PCQD-Al-15, PCQD-Al-16 or PCQD-Al-17 prepared by the method described in example 12. The reaction results are shown in Table 13.
Watch 13
| Test examples | Aluminum-based catalyst | Carbon source used | Conversion of FA/% | IPL yield/% |
| 13-1 | PCQD-Al-15 | Cellobiose | 99.1 | 96.8 |
| 13-2 | PCQD-Al-16 | Xylose | 100 | 97.7 |
| 13-3 | PCQD-Al-17 | Fructose | 100 | 97.8 |
| 9-1 | PCQD-Al-1 | Glucose | 100 | 97.7 |
As can be seen from Table 13, in addition to the slightly inferior alcoholysis activity of PCQD-Al-15 prepared from cellobiose, PCQD-Al-16 and PCQD-Al-17 prepared from two other monosaccharides, xylose and fructose, have the same alcoholysis activity as that of PCQD-Al-1 prepared from glucose, and excellent IPL yield was obtained.
Test example 14 (14-1 to 14-17): this test example examines the reaction conditions and the influence of alcohol solvent species on the alcoholysis conversion of Furfuryl Alcohol (FAL) to Levulinate Esters (LES) according to the evaluation method described in test example 9 using PCQD-Al-1 as a catalyst. The reaction results are shown in Table 14.
TABLE 14
As can be seen from Table 14, the alcoholysis reaction temperature, time, catalyst amount, isopropanol amount, and the use of different alcohol solvents all affected the yield of Levulinate Esters (LES) synthesized by alcoholysis of furfuryl alcohol catalyzed by PCQD-Al-1 to different degrees, and the optimized conditions were 0.1g of catalyst, 3.8mL of Isopropanol (IPA) as alcohol medium, and the reaction temperature and time were 120 deg.C and 10h, respectively.
Test example 15: this test example examines the stability of PCQD-Al-1 to catalyze the alcoholysis conversion of Furfuryl Alcohol (FAL) to isopropyl acetoacetate (IPL) in an isopropanol medium according to the evaluation method described in test example 9. The catalyst after each reaction is filtered and washed with IPA and then directly used for the next reaction, and after 5 times of reaction operation, the recovered catalyst is firstly dissolvedAdding proper amount of AlCl into 2M hydrochloric acid solution 3 .6H 2 O (20% by mass of the amount of the recovered catalyst) was added, and the regenerated catalyst was obtained by the treatment method described in step (2) of example 8 and then used in the 6 th alcoholysis reaction. The reaction results are shown in Table 15.
Watch 15
| State of use of catalyst | Number of reaction times | FAL conversion/% | IPL yield/% |
| Fresh and fresh | 1 | 100 | 97.7 |
| For the first time of recovery | 2 | 94.1 | 88.3 |
| For the second recovery | 3 | 81.4 | 75.4 |
| Recovered for the third time | 4 | 66.3 | 61.6 |
| Recovered for the fourth time | 5 | 63.2 | 59 |
| Fourth recovery and regeneration | 6 | 100 | 91.7 |
As can be seen from Table 15, the alcoholysis activity of GluPC-Al-1 continued to decrease with the increase in the number of alcoholysis reactions, indicating that there was a gradual deactivation of the catalyst. The alcoholysis activity of the regenerated catalyst recovered to about 94% of the fresh catalyst after 5 runs of the alcoholysis reaction.
Example 13 (13-1 to 13-4)
The method for preparing the phosphoric acid carbamic acid functionalized carbon dot-zirconium hybrid catalyst by taking carbohydrate as a raw material specifically comprises the following steps: the preparation process described In example 2 was followed, except that the glucose feedstock was replaced with inulin, starch, sucrose and fructose, respectively, in operation (1), thereby preparing PCQD-Zr-In, PCQD-Zr-St, PCQD-Zr-Su and PCQD-Zr-Fr-1.
Test examples 16 (16-1 to 16-9): the method for evaluating the synthesis of gamma-valerolactone (gamma-GVL) by Catalytic Transfer Hydrogenation (CTH) of Levulinic Acid (LA) in isopropanol in the test example specifically comprises the following steps: a10 mL hydrothermal crystallization kettle (polytetrafluoroethylene lining and stainless steel jacket) is used as a reactor. 5mmol of LA,0.05g of BCQD-Zr-1 synthesized In example 1, gluPC-Zr-Gu-1 synthesized In example 2, PCQD-Zr-In synthesized In examples 13-1 to 13-4, PCQD-Zr-St and PCQD-Zr-Fr-1 synthesized In example 1, and Zr (OH) synthesized In comparative example 1 were taken 4 And commercial ZrCl 4 、ZrO 2 Catalyst, 2.67mL Isopropanol (IPA, 35 mmol) was added to the batchIn the liner. It was placed in an oil bath pan which had been heated to 180 ℃ and reacted for 12h with stirring. After the reaction, the reactor was placed in a flowing cold air stream to be cooled to room temperature, the reaction solution was filtered using a 5 mL syringe and a 0.22 μm organic frit, and the filtered reaction solution was injected into a vial for vapor phase detection, and the product yield was calculated by the internal standard method using n-dodecane as an internal standard substance. The reaction results are shown in Table 16.
TABLE 16
As can be seen from Table 16, various carbohydrate-derived phosphoric acid carbamic acid carbon site coordinated zirconium-based catalysts generally showed excellent CTH activity, wherein PCQD-Zr-Gu-1 and PCQD-Zr-Fr-1 synthesized from two monosaccharides glucose and fructose showed the best CTH activity, and the yield of the target product gamma-GVL was as high as 95 and 95.6%, which is much higher than the result of catalyzing this CTH reaction by 3 commercial zirconium compounds.
Example 14 (14-1 to 14-4)
The method for preparing the phosphoric acid carbamate functionalized carbon dot-zirconium hybrid catalyst described in this embodiment specifically includes the following steps: the process as described in example 2 was followed, except that fructose was used as the starting material in the operation step (1) and the amounts of concentrated phosphoric acid and urea were changed so that the molar ratios of fructose, concentrated phosphoric acid and urea were 1:1: 3. 1:3: 6. 1:2:4 and 1:2: thus, PCQD-Zr-Fr-2, PCQD-Zr-Fr-3, PCQD-Zr-Fr-4 and PCQD-Zr-Fr-5 were prepared.
Test example 17 (17-1 to 17-4): the method for evaluating the synthesis of gamma-valerolactone (gamma-GVL) by Catalytic Transfer Hydrogenation (CTH) of Levulinic Acid (LA) in isopropanol in the test example specifically comprises the following steps: the evaluation methods described in test example 16 were conducted, except that the catalysts were used in the amounts of PCQD-Zr-Fr-2, PCQD-Zr-Fr-3, PCQD-Zr-Fr-4 and PCQD-Zr-Fr-5 prepared in example 14. The reaction results are shown in Table 17.
TABLE 17
As can be seen from table 17, fructose synthesized the PCQD ligand; phosphoric acid: the molar ratio of urea has influence on the preparation of the PCQD-Zr-Fr catalyst, and the PCQD ligand synthesized by using low phosphoric acid and/or urea dosage is not beneficial to preparing an excellent catalyst and preparing fructose optimized by the PCQD ligand; phosphoric acid: the molar ratio of urea is 1:2:6.
example 15 (15-1 to 15-4)
The method for preparing the phosphoric acid carbamate functionalized carbon dot-zirconium hybrid catalyst described in this embodiment specifically includes the following steps: the preparation as described in example 2 was followed, except that fructose was used instead as the starting material in operation (1) and ZrCl was changed in operation (2) 4 The amounts of (A) were 0.5 g and 1.0g, respectively, which were 1 times and 2 times the amount of GluPC by mass, thereby preparing PCQD-Zr-Fr-6 and PCQD-Zr-Fr-7.
Example 16 (16-1 to 16-3)
The method for preparing the phosphoric acid carbamate functionalized carbon dot-zirconium hybrid catalyst described in this embodiment specifically includes the following steps: the preparation method as described in example 2 was followed, except that the hydrothermal treatment process was omitted, the hydrothermal treatment temperature and/or the hydrothermal treatment time was changed (see the following table) in the operation step (2), thereby preparing PCQD-Zr-Gu-2, PCQD-Zr-Gu-3, PCQD-Zr-Gu-4, PCQD-Zr-Gu-5 and PCQD-Zr-Gu-6.
Test example 18 (18-1 to 18-7): the method for evaluating the synthesis of gamma-valerolactone (gamma-GVL) by Catalytic Transfer Hydrogenation (CTH) of Levulinic Acid (LA) in isopropanol in the test example specifically comprises the following steps: the evaluation methods described in test example 16 were conducted except that PCQD-Zr-Fr-6 and PCQD-Zr-Fr-7 prepared by the methods described in example 15 using catalysts, and PCQD-Zr-Gu-2, PCQD-Zr-Gu-3, PCQD-Zr-Gu-4, PCQD-Zr-Gu-5 and PCQD-Zr-Gu-6 prepared by the methods described in example 16 were used. The reaction results are shown in Table 18.
Watch 18
As can be seen from Table 18, zrCl 4 The increase of the PCQD/mass ratio, the CTH activity and the increase of the prepared PCQD-Zr-Fr; the CTH activity of PCQD-Zr-Gu-2 prepared without adopting hydrothermal treatment is poor, and the CTH activity of the PCQD-Zr-Gu can be generally improved to different degrees by adopting different hydrothermal treatment temperatures or times, and the proper ZrCl 4 The dosage is 1.5 times of the mass of the ligand PCQD, and the appropriate hydrothermal treatment temperature and time are 120 ℃ and 12h respectively.
Test example 19 (19-1 to 19-4): the evaluation method for synthesizing gamma-valerolactone (gamma-GVL) by Catalyzing Transfer Hydrogenation (CTH) of levulinic acid esters (LES) by PCQD-Zr-Fr-1 prepared in examples 13 to 4 in isopropanol in the test example specifically comprises the following steps: according to the evaluation method described in test example 16, LEs used were Methyl Levulinate (ML), ethyl Levulinate (EL), isopropyl levulinate (IPL) and n-Butyl Levulinate (BL). The reaction results are shown in Table 19.
Watch 19
| Test examples | The substrate used | LES conversion/% | gamma-GVL yield/% |
| 19-1 | Levulinic acid methyl ester (ML) | 99.9 | 98.8 |
| 19-2 | Ethyl Levulinate (EL) | 99.9 | 97.8 |
| 19-3 | Isopropyl levulinate (IPL) | 99.9 | 97.4 |
| 19-4 | Levulinic acid n-butyl ester (BL) | 99.9 | 93.6 |
As can be seen from Table 19, PCQD-Zr-Fr-1 also showed excellent CTH activity in the transfer hydrogenation of these levulinic acid esters, showing a tendency to decrease gradually with increasing carbon chain length in the levulinic acid esters, wherein in the transfer hydrogenation of ML, EL and IPL, yields of gamma valerolactone higher than 97% can be given.
Test examples 20 (20-1 to 20-3): the evaluation method of synthesizing gamma-valerolactone (gamma-GVL) from PCQD-Zr-Gu-1 prepared in example 2 in Catalysis of Transfer Hydrogenation (CTH) of Levulinic Acid (LA) described in the test example specifically comprises the following steps: according to the evaluation method described in test example 16, different secondary alcohol solvents used were 2-butanol, 2-pentanol and cyclohexanol, respectively. The reaction results are shown in Table 20.
Watch 20
| Test examples | The secondary alcohol solvent used | LA conversion/% | gamma-GVL yield/% | Levulinate yield/% |
| 20-1 | 2-Butanol | 95.2 | 68.7 | 23.8 |
| 20-2 | 2-pentanol | 92.3 | 57.3 | 32.9 |
| 20-3 | Cyclohexanol | 100 | 66.5 | 30.2 |
| 16-1 | Isopropyl alcohol | 100 | 95.3 | 2.0 |
As can be seen from Table 20, the secondary alcohol solvent has a significant influence on the PCQD-Zr-Fr-1 catalysis of the levulinic acid transfer hydrogenation reaction, and the CTH activity of the catalyst shows a trend of being obviously reduced along with the increase of the carbon chain of the secondary alkyl alcohol, wherein isopropanol is the most valuable hydrogen donor of the catalytic transfer hydrogenation reaction.
Test example 21 (21-1 to 21-14): in this test example, the effect of the reaction conditions on the synthesis of γ -valerolactone (γ -GVL) by transfer hydrogenation (CTH) of Levulinic Acid (LA) was examined by the evaluation method described in test example 16, using PCQD-Zr-Fu-1 prepared in example 13-4 as a catalyst, isopropyl alcohol (IPA) as a solvent, and a hydrogen donor. The reaction results are shown in Table 21.
TABLE 21
As can be seen from Table 21, the CTH reaction temperature, time, catalyst amount, isopropanol amount and Levulinic Acid (LA) amount all have different degrees of influence on the yield of gamma valerolactone (gamma-GVL) synthesized by PCQD-Zr-Fr-1 catalysis of levulinic acid transfer hydrogenation, the optimized conditions are 0.05g of catalyst, 2.67mL of Isopropanol (IPA) and 1-5mmol of LA, and the reaction temperature and the reaction time are respectively 180-190 ℃ and 10h.
Test example 22: this test example uses the solvent and hydrogen donor separately according to the evaluation method described in test example 16 to examine the reusability of PCQD-Zr-Fr-1 prepared in examples 13-4 in 5 runs of the catalytic hydrogenation synthesis of gamma-valerolactone (gamma-GVL) by transferring Levulinic Acid (LA) and Methyl Levulinate (ML) in an Isopropanol (IPA) medium. The catalyst reacted in each case was filtered and washed with IPA and used directly in the next reaction. The reaction results are shown in Table 22.
TABLE 22
As can be seen from Table 22, with the increase of the number of CTH reactions, the CTH activity of PCQD-Zr-Fr-1 in the synthesis of gamma-valerolactone by catalytic LA transfer hydrogenation gradually but slowly decreases, and the yield of gamma-valerolactone after 5 times of operation is still as high as 92% or more. The catalyst shows more excellent reusability in the CTH reaction of ML, and the yield of gamma-valerolactone after 5 times of operation is still as high as 96.5 percent.
Test example 23 (23-1 to 23-6): the evaluation method for one-pot synthesis of gamma-valerolactone (gamma-GVL) by alcoholysis and transfer hydrogenation (CTH) of Furfuryl Alcohol (FAL) in Isopropanol (IPA) described in this test example specifically comprises the following steps: the FAL is 1 mmol, PCQD-Al-1 and PCQD-Zr-Gu-1 mixed catalysts with different mass ratios are used, IPA is 4 mL, the reaction temperature of Furfuryl Alcohol (FAL) alcoholysis is 120 ℃, the reaction time is 8 hours, and then the temperature is raised to 180 ℃ to carry out CTH reaction for 10 hours. The reaction results are shown in Table 23.
TABLE 23
As can be seen from Table 23, the amount of PCQD-Al-1 and PCQD-Zr-Gu-1 in the mixed catalyst varied to have a large effect on the alcoholysis of Furfuryl Alcohol (FAL) in Isopropanol (IPA) and the one-pot reaction of transfer hydrogenation (CTH), giving a yield of gamma-valerolactone of up to 84% with the mixed catalyst of 0.075 g of PCQD-Al-1 and 0.05g of PCQD-Zr-Gu-1 combined (mass ratio 1.5.
Test example 24 (24-1 to 24-8): the evaluation method for one-pot synthesis of gamma-valerolactone (gamma-GVL) by alcoholysis and transfer hydrogenation (CTH) of Furfuryl Alcohol (FAL) in Isopropanol (IPA) described in the test example specifically comprises the following steps: FAL was 1 mmol, a mixed catalyst (mass ratio: 1.5: 1) of 0.075 g of PCQD-Al-1 and 0.05g of PCQD-Zr-Gu-1 was used, IPA was 4 mL, the reaction temperature for alcoholysis of Furfuryl Alcohol (FAL) was 90-130 ℃, the reaction time was 8 hours, the reaction temperature for CTH was 150-180 ℃, and the reaction time was 10 hours. The reaction results are shown in Table 24.
Watch 24
| Test examples | Alcoholysis temperature → CTH temperature/. Degree.C | FAL conversion/% | IPL yield/% | gamma-GVL yield/% |
| 24-1 | 90→180 | 96.6 | 9.1 | 74.4 |
| 24-2 | 100→180 | 98.4 | 2.0 | 81.2 |
| 24-3 | 110→180 | 98.2 | 1.2 | 88.8 |
| 23-5 | 120→180 | 99.0 | 6.4 | 84.0 |
| 24-4 | 130→180 | 97.6 | 0.6 | 80.9 |
| 24-5 | 110→150 | 97.9 | 63.2 | 27.9 |
| 24-6 | 110→160 | 97.3 | 44.0 | 46.4 |
| 24-7 | 110→170 | 98.5 | 3.2 | 80.3 |
| 24-8 | 110→190 | 100 | 0.9 | 88.9 |
As can be seen from Table 24, the choice of alcoholysis combined with transfer hydrogenation (CTH) reaction temperature has a large impact on the PCQD-Al-1 and PCQD-Zr-Gu-1 mixtures catalyzing the one-pot conversion of Furfuryl Alcohol (FAL) in Isopropanol (IPA), giving γ -valerolactone yields of up to 88.8 and 88.9% at alcoholysis temperature of 110 ℃ and CTH temperature of 180 ℃ or 190 ℃.
Test example 25 (25-1 to 25-3): the evaluation method for one-pot synthesis of gamma-valerolactone (gamma-GVL) by alcoholysis and transfer hydrogenation (CTH) of Furfuryl Alcohol (FAL) in Isopropanol (IPA) described in the test example specifically comprises the following steps: FAL is 1 mmol, a mixed catalyst (mass ratio is 1.5. The reaction results are shown in Table 25.
TABLE 25
| Test examples | IPA dosage/mL | FAL conversion/% | IPL yield/% | gamma-GVL yield/% |
| 25-1 | 2 | 96.5 | --- | 51.3 |
| 25-2 | 3 | 97.8 | --- | 63.5 |
| 24-3 | 4 | 98.2 | 1.2 | 88.8 |
| 25-3 | 5 | 97.3 | 0.7 | 79.4 |
As can be seen from Table 25, the amount of isopropyl alcohol (IPA) solvent used had a large effect on the one-pot conversion of Furfuryl Alcohol (FAL) catalyzed by the PCQD-Al-1 and PCQD-Zr-Gu-1 mixtures, giving a maximum yield of 88.8% gamma valerolactone at an IPA level of 4 mL.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (5)
1. A method for preparing a biomass-derived functionalized carbon dot-metal hybrid catalytic material, the method comprising the steps of: (1) Carrying out hydro-thermal treatment on biomass by using a sodium hydroxide solution to obtain a hydroxyl-functionalized biomass carbon dot BCQD solution; (2) Mixing the BCQD aqueous solution obtained in the step (1) with ZrCl 4 Mixing the aqueous solutions, and then carrying out hydrothermal treatment on the mixed solution at a certain temperature and pH value for 12h to obtain a hybrid catalytic material BCQD-Zr;
the biomass used for preparing the BCQD in the step (1) is one of bamboo powder, wood powder, fruit peel and tea residue, the used sodium hydroxide is 60-100% of the biomass amount by mass, the hydrothermal treatment temperature is 180-200 ℃, and the hydrothermal treatment time is 9-12 hours;
ZrCl described in step (2) 4 The dosage is 1 to 1.75 times of the dosage of the BCQD by mass, the pH value of the mixed solution is 1~3, the hydrothermal treatment temperature is 120 to 150 ℃, and the hydrothermal treatment time is 6 to 20 hours;
the BCQD-Zr is used for catalyzing the reaction of converting furfural into furfuryl alcohol in a secondary alcohol medium or catalyzing the reaction of converting levulinic acid and levulinate ester into gamma-valerolactone in the secondary alcohol medium; the secondary alcohol is isopropanol or 2-butanol.
2. Use of the biomass-derived functionalized carbon dot-metal hybrid catalytic material prepared according to the preparation method of claim 1 for catalyzing the conversion of furfural into furfuryl alcohol in a secondary alcohol medium or for catalyzing the conversion of levulinic acid and levulinate esters into gamma valerolactone in a secondary alcohol medium.
3. The application of the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material in catalyzing furfural to be converted into furfuryl alcohol in a secondary alcohol medium is characterized in that the preparation method of the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material is as follows: (1) Carrying out heat treatment on carbohydrate by using concentrated phosphoric acid and urea to obtain phosphoric acid and carbamic acid functionalized carbon point PCQD aqueous solution; (2) Mixing the PCQD aqueous solution obtained in the step (1) with ZrCl 4 Mixing the aqueous solutions, and then carrying out hydrothermal treatment on the mixed solution at a certain temperature and pH value for 12h to obtain a hybrid catalytic material PCQD-Zr;
in the step (1), the carbohydrate used for preparing the PCQD is one of glucose, fructose, xylose, sucrose, inulin and starch, the mass ratio of the carbohydrate used for preparing the PCQD to concentrated phosphoric acid to urea is 1 to 2 to 1, the heat treatment temperature is 135 ℃, and the heat treatment time is 2 h;
ZrCl described in step (2) 4 The dosage is 1 to 1.75 times of the dosage of the PCQD by mass, the pH value of the mixed solution is 1~3, the hydrothermal treatment temperature is 120 to 150 ℃, and the hydrothermal treatment time is 6 to 20 hours;
the secondary alcohol is isopropanol or 2-butanol.
4. The application of the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material in alcoholysis catalysis of furfuryl alcohol converted into levulinate in an alcohol medium is characterized in that the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material is prepared by the following steps: (1) Carrying out heat treatment on carbohydrate by using concentrated phosphoric acid and urea to obtain phosphoric acid and carbamic acid functionalized carbon point PCQD aqueous solution; (2) Will step withThe PCQD aqueous solution obtained in the step (1) and AlCl 3 Mixing the aqueous solutions, and then carrying out hydrothermal treatment on the mixed solution at a certain temperature and pH value for 12h to obtain a hybrid catalytic material PCQD-Al;
the carbohydrate used for preparing the PCQD in the step (1) is one of glucose, fructose, xylose, sucrose, inulin and starch, the mass ratio of the carbohydrate, concentrated phosphoric acid and urea used for preparing the PCQD is 1 to 2 to 1, the heat treatment temperature is 135 ℃, and the heat treatment time is 2 h;
in the step (2), the AlCl 3 The dosage is 1 to 3.4 times of that of the PCQD by mass, the pH value of the mixed solution is 1~3, the hydrothermal treatment temperature is 120 to 150 ℃, and the hydrothermal treatment time is 6 to 20 hours;
the alcohol medium is methanol, ethanol, isopropanol or n-butanol.
5. The application of the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material in the one-pot synthesis of gamma-valerolactone by alcoholysis and transfer hydrogenation of furfuryl alcohol in isopropanol is characterized in that the preparation method of the carbohydrate derived functionalized carbon dot-metal hybrid catalytic material comprises the following steps: (1) Carrying out heat treatment on carbohydrate by using concentrated phosphoric acid and urea to obtain phosphoric acid and carbamic acid functionalized carbon point PCQD aqueous solution; (2) Respectively mixing the PCQD aqueous solution obtained in the step (1) with ZrCl 4 、AlCl 3 Mixing the aqueous solutions, and then performing hydrothermal treatment on the mixed solution at a certain temperature and pH value to obtain 12h respectively to obtain hybrid catalytic materials PCQD-Zr and PCQD-Al; (3) And mixing the PCQD-Zr and the PCQD-Al to prepare the hybrid catalytic material.
In the step (1), the carbohydrate used for preparing the PCQD is one of glucose, fructose, xylose, sucrose, inulin and starch, the mass ratio of the carbohydrate used for preparing the PCQD to concentrated phosphoric acid to urea is 1 to 2 to 1, the heat treatment temperature is 135 ℃, and the heat treatment time is 2 h; zrCl described in step (2) 4 The dosage is 1 to 1.75 times of the dosage of PCQD by mass, and the AlCl is added 3 The dosage is 1 to 3.4 times of that of the PCQD by mass, the pH value of the mixed solution is 1~3, the hydrothermal treatment temperature is 120 to 150 ℃, and the hydrothermal treatment time is 6 to 20 hours.
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