CATALYTIC TEST PAPER PREPARED BY COMPOSITING METAL PARTICLE-EMBEDDED BACTERIAL CELLULOSE WITH PLANT FIBERS, AND METHOD THEREFOR

Abstract

Disclosed is a catalytic test paper prepared by compositing metal particle-embedded bacterial cellulose with plant fibers, and a preparation method therefor. Hydroxyl groups of bacterial cellulose are bonded with a nitrogen-containing or phosphorus-containing organic small molecule compound. By means of a chelation between a nitrogen or phosphorus atom with a metal, transition metal ions are adsorbed to a nanoporous surface of bacterial cellulose, and the transition metal ions are reduced in situ to obtain bacterial cellulose embedded with metal nanoparticles. The bacterial cellulose is composited with the plant fiber, and the catalytic test paper is prepared by a papermaking method. The catalytic test paper has the advantages of convenient use and recovery, high reusability, simple design, low manufacturing cost, higher catalytic efficiency, a green degradable support material, etc.

Claims

1. A method for preparing a catalytic test paper by compositing metal particle-embedded bacterial cellulose with plant fibers, characterized in that, the method comprises the following steps: (1) chemically bonding a nitrogen-containing or phosphorus-containing organic small molecule compound with hydroxyl groups in a structure of bacterial cellulose to obtain a functionalized bacterial cellulose having a nitrogen or phosphorus-containing group; (2) preparing an aqueous solution of an inorganic salt of a transition metal, adding the aqueous solution into the functionalized bacterial cellulose prepared in the step (1), stirring and reacting according to a solubility of the inorganic salt of the transition metal until the nitrogen-containing or phosphorus-containing group adsorbs transition metal ions onto a nanoporous surface of the bacterial cellulose till saturation, separating and washing with water; (3) reducing the transition metal ions adsorbed on the surface of the bacterial cellulose in the step (2) in situ to obtain bacterial cellulose embedded with transition metal nanoparticles; and (4) mixing a plant fiber pulp with the bacterial cellulose embedded with the transition metal nanoparticles prepared in the step (3), then uniformly dispersing the mixed pulp, manufacturing the mixed pulp into a paper, and then drying the paper to an equilibrium weight to obtain the catalytic test paper.

2. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, the bacterial cellulose in the step (1) is secreted in vitro by a bacterial microorganism, and a culturing condition is a static or dynamic fermentation culturing condition; the bacterial microorganism is one of gluconacetobacter, acetobacter, agrobacterium, pseudomonas, achromobacter, alcaligenes, aerobacter, azotobacter, rhizobium and sarcina; and the nitrogen-containing or phosphorus-containing organic small molecule compound is one or more of ethylenediamine, tetraethylenepentamine, diethylenetriamine, polyethyleneimine, N-methylimidazole and chlorodiphenyl phosphine.

3. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, a method for bonding the nitrogen-containing or phosphorus-containing organic small molecule compound with the hydroxyl groups of the bacterial cellulose in the step (1) is to oxidize the hydroxyl groups on the bacterial cellulose into aldehyde groups in water by using an oxidant, and then bond the aldehyde groups with the nitrogen-containing compound through a reductive amination reaction; and the oxidant is one or more of a periodate or a 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) agent.

4. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, a method for bonding the nitrogen-containing or phosphorus-containing organic small molecule compound with the hydroxyl groups of the bacterial cellulose in the step (1) is to react the bacterial cellulose with a halogen-containing epoxy compound in concentrated alkaline with a mass concentration of 10% to 20%, to bond epoxy groups with the hydroxyl groups of the bacterial cellulose, and then to react the epoxy groups with the nitrogen-containing organic small molecule compound.

5. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, a method for bonding the nitrogen-containing or phosphorus-containing organic small molecule compound with the hydroxyl groups of the bacterial cellulose in the step (1) is to react the bacterial cellulose with thionyl chloride under dimethylformamide or N,N-dimethylacetamide, to bond chlorine atoms to the hydroxyl groups of the bacterial cellulose, and then to react with the nitrogen-containing organic small molecular compound.

6. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, a method for bonding the nitrogen-containing or phosphorus-containing organic small molecule compound with the hydroxyl groups of the bacterial cellulose in the step (1) is to bond with the hydroxyl groups of the bacterial cellulose by using chlorodiphenyl phosphine in a condition that pyridine is used as a solvent.

7. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, the transition metal in the step (2) is one or more of palladium, chromium, nickel, silver, copper and gold.

8. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, a method for reducing the transition metal ions adsorbed by the bacterial cellulose in situ in the step (3) is to soak the bacterial cellulose adsorbed with the transition metal ions in a solution of a sodium borohydride, sodium cyanoborohydride or hydroxylamine hydrochloride reducing agent.

9. The method for preparing the catalytic test paper by compositing the metal particle-embedded bacterial cellulose with the plant fibers according to claim 1, characterized in that, the plant fiber pulp in the step (4) is a papermaking raw material prepared from a wood fiber, a non-wood plant fiber or a secondary fiber by a mechanical or chemical pulping method.

10. A catalytic test paper prepared by the preparation method according to claim 1.

11. A catalytic test paper prepared by the preparation method according to claim 2.

12. A catalytic test paper prepared by the preparation method according to claim 3.

13. A catalytic test paper prepared by the preparation method according to claim 4.

14. A catalytic test paper prepared by the preparation method according to claim 5.

15. A catalytic test paper prepared by the preparation method according to claim 6.

16. A catalytic test paper prepared by the preparation method according to claim 7.

17. A catalytic test paper prepared by the preparation method according to claim 8.

18. A catalytic test paper prepared by the preparation method according to claim 9.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 is a flow chart of a method for preparing a catalytic test paper by compositing metal particle-embedded bacterial cellulose with plant fibers.

DETAILED DESCRIPTION

[0029] The present invention is further described in detail through the embodiments hereinafter, but the implementation of the present invention is not limited to the embodiments.

[0030] Bacterial cellulose in the embodiment was secreted by Glucoacetobacter xylinus. Main components of a bacterial culturing medium included 50 mL of fermented coconut water, 0.1 g of ammonium sulfate, 0.1 g of magnesium sulfate, 0.1 g of potassium dihydrogen phosphate, 3.0 g of sucrose, and 50 mL of distilled water, and was adjusted to pH 4.1 with NaOH, and was sterilized at 100 C. for 5 minutes. The culturing medium was placed in a 250 mL beaker for static fermentation, inoculated with 5% (V/V) Glucoacetobacter xylinus, and stood and cultured at 30 C. for 6 days. A solid content of a wet bacterial cellulose pellicle obtained was 1.5 wt %.

Embodiment 1

[0031] 30 g of bacterial cellulose (BC) wet pellicle was cut into small pieces, added into 100 mL of water, separated into small fragments (2 mm in each direction) by using a tissue masher, till the small fragments were not suspended in water after stood for a period of time. The fragments were filtered, then added into 100 mL of 0.2% sodium periodate solution, and stirred at 350 rpm. A reaction was performed at a room temperature for 2 days without light. After the reaction was completed, an oxidized bacterial cellulose was filtered and washed. The oxidized bacterial cellulose was mixed with 5.6 g of polyethyleneimine and 80 mL of deionized water into a conical flask. 0.21 g of sodium cyanoborohydride was added as a catalyst. A pH of the mixture was added to 5.8 to 6 with 0.1 M hydrochloric acid. A reaction was performed under magnetic stirring at 350 rpm at a room temperature for 6 hours. After the reaction, a polyethyleneimine-modified BC was filtered and washed.

[0032] 0.5 g of potassium chloropalladite (K.sub.2PdCl.sub.4) was dissolved in 100 ml of 70 C. hot water, and then added with the polyethyleneimine-modified BC. The mixture reacted at 70 C. for 6 hours under magnetic stirring at 350 rpm. The obtained solid product was washed with hot water and added into 100 mL of 5 mg/mL sodium borohydride solution to react at a room temperature for 1 hour, so as to reduce a supported palladium ion in situ. The obtained palladium nanoparticle-embedded BC (Pd-BC) was filtered and washed with deionized water. A mass fraction of palladium supported by the Pd-BC reached 9.7%.

[0033] The Pd-BC was mixed with bleached bagasse pulp at a mass ratio of 20% (the Pd-BC in a dry weight of paper), and uniformly dispersed with a standard paper pulp disintegrator at a consistency of 1% (m/m). Catalytic test paper was made of the mixed pulp by a standard paper handsheet former (Messmer 225, Holland). A dry weight of each sheet was controlled at 70 g/m.sup.2. The paper sheet was dried at 120 C. for 20 minutes and kept away from light and air.

[0034] The catalytic test paper had a good catalytic effect on a Suzuki-Miyaura coupling reaction. 2 mmol of K.sub.2CO.sub.3 was used as alkali, and 16 mL of 95% ethanol, 1.1 mmol of phenylboronic acid and 1 mmol of iodobenzene were used to study a catalytic reaction which generated biphenyl at 80 C. in a 20 mL vial with a screw cap. All reactions were performed under a normal atmospheric condition without an inert gas atmosphere. After a solvent and a chemical were added, the reaction vial was closed with the cap and added into an oil bath that was preheated to 80 C. The catalytic test paper was cut into 1 cm3 cm pieces. Four pieces of paper were used for each reaction and placed in a nylon net frame. After a temperature of the reaction vial in the oil bath reached equilibrium, the nylon frame loaded with the catalytic paper was inserted, the cap of the vial was closed to prevent air from entering, and the reaction mixture was stirred with a magnetic stirring rod. A yield of the biphenyl after the reaction for 2 hours was 99%. When the same catalytic test paper was used for 26 times, the yield thereof could still be close to 90%. In the same way, several phenylboronic acids and aryl halides with different substituents were selected, and the catalytic test paper also had a good catalytic efficiency. A catalytic reaction time and a yield were shown in Table 1 below (a reaction time and a yield of using the catalytic test paper in Embodiment 1 for generating a biphenyl product with 1 mmol of phenylboronic acid and 1.1 mmol of aryl halide by using 2.5 mmol of K.sub.2CO.sub.3 as an alkali in 16 mL of 95% ethanol, wherein a reaction temperature was 80 C.).

TABLE-US-00001 TABLE 1 [Chemical formula 1] [00001] [00002] Reaction Yield X R.sup.1 R.sup.2 time h % I H H 1.5 95 I 4-COCH.sub.3 H 1.5 100 I 4-NO.sub.2 H 1.5 100 I 4-NH.sub.2 H 3(8) 15(80) I 4-CH.sub.3 H 1.5 98 I 4-OCH.sub.3 H 3 98 I H Cl 3 42 I H OCH.sub.3 3 36 Br H H 3(6) 56(76) Br 4-COCH.sub.3 H 3 91 Br 4-NO.sub.2 H 2 99 Br 4-NH.sub.2 H 3 90 Br 4-CH.sub.3 H 3 60 Br 4-OCH.sub.3 H 3(8) 66(72) Note: X = halogen; R = substituent on benzene ring.

Embodiment 2

[0035] 30 g of bacterial cellulose (BC) wet pellicle was cut into small pieces, added into 90 mL of deionized water, separated into small fragments (2 mm in each direction) by using a tissue masher, till the small fragments were not suspended in water after stood for a period of time. The fragments were filtered, then added into 10% sodium hydroxide solution for swelling, and stirred at 350 rpm for 20 minutes. 15 mL of epoxy chloropropane was added, and then the mixture was filtered and washed after reaction for 24 hours. The epoxidized BC was added into 90 mL of deionized water, and added with 7.6 mL of tetraethylenepentamine and 1.3 g of sodium carbonate. The mixture was filtered and washed after reaction for 3 hours at a room temperature to obtain a tetraethylenepentamine-modified BC.

[0036] 0.5 g of potassium chloropalladite (K.sub.2PdCl.sub.4) was dissolved in 100 ml of 80 C. hot water, and then added with the tetraethylenepentamine-modified BC. The mixture reacted at 80 C. for 3 hours under magnetic stirring at 350 rpm. The obtained solid product was washed with hot water and added into 100 mL of 5 mg/mL sodium borohydride solution to react at a room temperature for 1 hour, so as to reduce a supported palladium ion in situ. The obtained palladium nanoparticle-embedded BC (Pd-BC) was filtered and washed with deionized water. A mass fraction of palladium supported by the Pd-BC reached 8.2%.

[0037] The Pd-BC was mixed with bleached bagasse pulp at a mass ratio of 20% (the Pd-BC in a dry weight of paper), and uniformly dispersed with a standard paper pulp disintegrator at a consistency of 1% (m/m). Catalytic test paper was made of mixed paper pulp by a standard paper handsheet former (Messmer 225, Holland). A dry weight of each piece of paper was controlled at 70 g/m.sup.2. The paper was dried at 105 C. for 30 minutes and kept away from light and air.

[0038] The catalytic test paper had a good catalytic effect on a Heck reaction and a Sonogashira reaction. 2 mmol of K.sub.2CO.sub.3 was used as alkali, and 16 mL of 95% ethanol, 1.1 mmol of styrene or 1.1 mmol of phenylethynyl, and 1 mmol of bromobenzene were used to study a reaction at 80 C. in a 20 mL vial with a screw cap. All reactions were performed under a normal atmospheric condition without an inert gas atmosphere. After a solvent and a chemical were added, the reaction vial was closed with the cap and added into an oil bath that was preheated to 80 C. The catalytic test paper was cut into 1 cm3 cm pieces. Four pieces of paper were used for each reaction and placed in a nylon net frame. After a temperature of the reaction vial in the oil bath reached equilibrium, the nylon frame loaded with the catalytic paper was inserted, the cap of the vial was closed to prevent air from entering, and the reaction mixture was stirred with a magnetic stirring rod. Yields after reaction for 2 hours were 95% and 98% respectively. When the same catalytic test paper was used for 20 times, the yield thereof could still be close to 90%.

Embodiment 3

[0039] 30 g of bacterial cellulose (BC) wet pellicle was cut into small pieces, and the step was the same as that in the Embodiment 1. BC water was filtered, then added into 100 mL of pyridine, heated to 80 C., and stirred at 500 rpm for 30 minutes. After cooling to a room temperature, 10 mL of chlorodiphenyl phosphine was added to react at 350 rpm at a room temperature for 3 days. After the reaction was completed, the mixture was filtered and washed to obtain a diphenylphosphine functionalized BC. The diphenylphosphine functionalized BC was added into 100 mL of 0.2 M nickel chloride hexahydrate solution (NiCl.sub.2.6H.sub.2O), and stirred at 350 rpm at a room temperature for 4 hours. The solid product was filtered and washed, added into 100 mL of 0.1 M sodium cyanoborohydride solution, and stirred and reacted at a normal temperature for 1 hour to reduce a supported nickel ion in situ. An obtained nickel-nanoparticle-supported BC (Ni-BC) was filtered and washed with deionized water.

[0040] The Ni-BC was mixed with bleached softwood pulp to manufacture the catalytic test paper, and the step was the same as that in the Embodiment 1.

[0041] The catalytic test paper had a good catalytic effect on a degradation reaction of a nitro-aromatic compound. 0.8 mL of 0.2 M 2-nitrophenol solution, 1.6 mL of 0.2 M sodium borohydride solution and 10 mL of deionized water were added into a 20 mL vial with a screw cap to react at a room temperature. A usage method and a dosage of the catalytic test paper were the same as those in the Embodiment 1. A yield of 2-aminophenol after reaction for 30 minutes was 92%, When the same catalytic test paper was used for 10 times, the yield thereof could still be close to 85%.

Embodiment 4

[0042] 30 g of bacterial cellulose (BC) wet pellicle was cut into small pieces, and the step was the same as the Embodiment 1. The BC was added into a mixed solution of 100 mL of N,N-dimethylacetamide and 20 mL of thionyl chloride, and stirred at 95 C. for 3 hours to prepare a chlorinated BC. 3.28 g of N-methylimidazole was added into 100 mL of dimethyl sulfoxide (DMSO), added with the chlorinated BC after dissolution, heated to 100 C. under protection of inert gas, and stirred at 350 rpm for 12 hours. After cooling to a room temperature, the mixture was filtered and washed with acetone to obtain a N-methylimidazole-functionalized BC. The N-methylimidazole-functionalized BC was added into 100 mL of 0.1 M silver nitrate solution (AgNO.sub.3), and reacted at 350 rpm at a room temperature for 4 hours. The obtained solid product was filtered and washed, added into 100 mL of 0.1 M sodium cyanoborohydride solution, and stirred and reacted at a normal temperature for 1 hour to reduce a supported silver ion in situ. An obtained silver-nanoparticle-supported BC (Ag-BC) was filtered and washed with deionized water.

[0043] The Ag-BC was mixed with secondary fiber wood pulp to manufacture the catalytic test paper, and the step was the same as that in the Embodiment 1.

[0044] The catalytic test paper had a good catalytic effect on a degradation reaction of a nitro-aromatic compound. 0.8 mL of 0.2 M 4-nitrophenol solution, 1.6 mL of 0.2 M sodium borohydride solution and 10 mL of deionized water were added into a 20 mL vial with a screw cap to react at a room temperature. A usage method and a dosage of the catalytic test paper were the same as those in the Embodiment 1. A yield of 4-aminophenol after reaction for 30 minutes was 95%, When the same catalytic test paper was used for 10 times, the yield thereof could still be close to 90%.

[0045] A flow chart of the present invention is shown in FIG. 1.

[0046] The embodiments enumerated above are only specific embodiments of the present invention. The present invention is not limited to the above embodiments, and may also have many variations. Any variations that are able to be directly derived from or associated with the disclosure of the present invention by those of ordinary skills in the art shall be regarded as falling within the scope of protection of the present invention.