CN102814198B - A kind of Metal/grapheme nanocatalyst and its preparation method and application - Google Patents
A kind of Metal/grapheme nanocatalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Metal/grapheme nanocatalyst and its preparation method and application.It comprises Graphene and the metal nanoparticle of load on it, and its dispersiveness in DMF or water is high.The present invention, by being mixed in the DMF solution containing organic negative hydrogen donor with metal ion by the Graphene of graphene oxide or chemical functionalization, is obtained Metal/grapheme nanocatalyst by organic negative hydrogen donor reduction afterwards under illumination condition; This synthetic method step is simple, under the condition not adding any surfactant, can successfully by undersized metal nanoparticle equably load on Graphene.Metal/grapheme nanocatalyst prepared by the present invention all has excellent catalytic performance in organic synthesis and optical drive hydrogen manufacturing.
Description
Technical field
The invention belongs to catalysis technical field, particularly a kind of Metal/grapheme nanocatalyst and its preparation method and application.
Background technology
Platinum group metal nano material is as widely used catalyst in petroleum industry, purifying vehicle exhaust, fuel cell equal energy source and environment major areas.The surface of the platinum of carbon load, ruthenium and palladium metal nano particle has stronger adsorption activity (especially to hydrogen atom and hydrogen) and good electron storage performance and transmission performance, it is made to have excellent catalytic performance, therefore the catalyst in chemical industry is widely used in, especially as the eelctro-catalyst in fuel cell.But because the reserves of platinum group metal are rare, how improving the activity and selectivity of platinum based catalyst, thus reduce the consumption of platinum group metal, is the problem that this field receives much concern always.
Research shows that the metallic of nano-scale has very high catalytic activity, especially for electrochemical catalyst.The catalytic activity of metal has very large relation with its size on the one hand.For platinum group metal, the optimum size that catalytic activity requires is 3nm.Therefore the size of platinum group metal nano particle controlled well can not only improve the utilization rate of this kind of noble metal, and it can be made to play best catalytic effect.Although there be a large amount of reporting about the research controlling platinum group metal nano-particles size in the solution at present; the overwhelming majority research all employ can form micella surfactant as alkyl hydrosulfide in case tablet submanifold assemble; but these protectiveness parts can cover some catalytic site of nano particle undoubtedly, can weaken its catalytic effect undoubtedly.Thus be necessary to find method novel, energy synthetic surface " totally ", undersized metal nanoparticle.
On the other hand, the performance of catalyst carrier to catalyst also has a great impact.Activated carbon, XC-72 nano-sized carbon, CNT etc. are all some conventional catalyst carriers.CNT, because of its good conductivity, can be assembled and transmission electronic, effectively can suppress electronics and the hole compound in semiconductor, and its this separation of charge effect has been applied to the field of photovoltaic solar cell and organic dyestuff photocatalysis product hydrogen.As carrier, different material with carbon elements has a great impact, especially for eelctro-catalyst because of the catalytic performance of difference to platinum group metal nano particle of its pattern and electronic transmission performance.In order to strengthen the catalytic performance of platinum group metal nano particle further, being necessary to research and develop a kind of new material with carbon element carrier, being distributed on carrier while metal nanoparticle energy high uniformity can be made.The Graphene of nearest discovery is a kind of novel Two-dimensional Carbon material, and it is by the former molecular two dimensional crystal of monolayer carbon, because it has excellent electrical conductance, and thermal conductance and mechanical performance, and very large specific area and be subject to extensive concern.Thus, the Metal/grapheme nanocatalyst that we can predict by Graphene and metallic catalyst compound being obtained is the novel material with high catalytic activity of a class.Have now been developed the method for a lot of graphene-supported metallic, but most research is based on absorption-reducing process, namely graphene oxide is mixed with the solution of slaine, thus make slaine be adsorbed onto graphenic surface, and then reducing agent in solution or high temperature reduction in reducing atmosphere, obtain graphene-supported metallic.But this method is difficult to the size controlling metal nanoparticle, and often need to add dispersant in reaction, the Graphene dispersiveness in aqueous that obtains of simultaneously reducing is also poor, brings the unfavorable result of lower degradation of light scattering, filter effect and catalyst effective ratio area thereupon.
Given this, be necessary that development is under the condition not adding any surfactant, just can load to the straightforward procedure on carrier equably by undersized metal nanoparticle.
Summary of the invention
First technical problem that the present invention will solve is to provide a kind of Metal/grapheme nanocatalyst; This catalyst comprises the metal nanoparticle of Graphene and load on it; This catalyst is dispersed high in DMF (DMF) or water, has using value in fields such as Photocatalyzed Hydrogen Production, reducing carbon dioxide, organic catalysis.
Second technical problem that the present invention will solve is to provide a kind of preparation method of Metal/grapheme nanocatalyst; The method, by being mixed in DMF/ water mixed solvent with metal ion by Graphene, is obtained Metal/grapheme nanocatalyst by organic negative hydrogen donor reduction afterwards under illumination condition; This synthetic method step is simple, under the condition not adding any surfactant, can successfully by undersized metal nanoparticle equably load on Graphene.
The 3rd technical problem that the present invention will solve is to provide a kind of application of Metal/grapheme nanocatalyst; It can be used for organic synthesis and optical drive hydrogen production reaction.
For solving above-mentioned first technical problem, the invention provides a kind of Metal/grapheme nanocatalyst, it comprises the metal nanoparticle of Graphene and load on it; Described Graphene is the graphene oxide of graphene oxide or chemical functionalization; Described Metal/grapheme nanocatalyst has surface heterogeneous medium junction structure.
Described graphene oxide can be obtained by other known methods, only need meet the good dispersion of obtained graphene oxide in water, the invention provides a kind of preferred preparation method.
Described graphene oxide obtains through the following steps:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9 ~ 15ml concentrated sulfuric acid, is heated to 75 ~ 85 DEG C until potassium persulfate and phosphorus pentoxide all dissolve; Then add 1.8 ~ 2.2g graphite, at 75 ~ 85 DEG C of temperature, react 4 ~ 5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite obtained by step a joins in 75 ~ 85ml concentrated sulfuric acid of ice bath cooling, slowly adds 8 ~ 12g potassium permanganate under under magnetic stirring in this mixture, then at 30 ~ 40 DEG C, reacts 3 ~ 5h, reacts 1.5 ~ 2.5h again under room temperature; Slowly add the deionized water of 150 ~ 170ml, keep temperature to be no more than 50 DEG C, continue stirring 1.5 ~ 2.5h; Add water and the 30wt% hydrogen peroxide 8 ~ 12ml of 450 ~ 490ml again, produce jonquilleous solution, after this solution places 24h, outwell supernatant, then by remaining liquid, first wash twice respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator, and then wash twice with 10wt%HCl, last dialysis 6 ~ 8 days in water, the solid obtained is dry at 45 ~ 55 DEG C, obtained graphite oxide;
C. graphite oxide is peeled off as mono-layer graphite olefinic oxide
The graphite oxide that step b is obtained is placed in deionized water, and through ul-trasonic irradiation 10 ~ 30min, ultrasonic power is 150W, dissociates and obtains the graphene oxide solution of individual layer; Described graphite oxide: deionized water is 0.3mg ~ 0.6mg: 1mL.
The graphene oxide of described chemical functionalization is on Graphene, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain; Wherein, the structure of P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain is as follows:
1) P-TOLUENE SULFO ACID 99's base:
2) aziridinyl acetal chain:
Describedly on Graphene, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain can be obtained by other known methods, the invention provides a kind of preferred method.
Described P-TOLUENE SULFO ACID 99's base of modifying on Graphene is realized by following steps:
Get graphene oxide solution 40ml, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10, add the sodium borohydride of 100 ~ 200g wherein, under the condition of 80 ~ 90 DEG C, react 1 ~ 2h, then centrifugal, after the solid washed with water obtained twice, then be distributed in water the dispersion liquid making 0.3 ~ 0.6mg/l; Add the hydrochloric acid diazol 3 ~ 6ml containing 0.095M p-sulfonic acid benzene wherein, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, precipitation is after centrifugation, wash three times with the acetone/water mixed solvent that volume ratio is 3: 1 again, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
Described aziridinyl acetal chain of modifying on Graphene is realized by following steps:
Get graphene oxide solution 50ml; the 1-METHYLPYRROLIDONE adding 30 ~ 40ml (is called for short: NMP) ultrasonic 1h later; bubbling argon degasification 20min; [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols of 1 ~ 3g are added under argon shield condition; put into oil bath reaction 10 ~ 20h for 160 DEG C; after being cooled to room temperature; solid DMF is washed three times; wash six times with acetone, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
Further, described metal nanoparticle is platinum, ruthenium or palladium.
For solving above-mentioned second technical problem, the invention provides a kind of preparation method of Metal/grapheme nanocatalyst, comprise the following steps: the Graphene of graphene oxide or chemical functionalization is mixed with the DMF solution containing organic negative hydrogen donor, add the aqueous solution of metal ion afterwards, deoxygenation, this system of illumination, adds extractant extraction organic matter, aqueous phase and pelleting centrifugation, the solid obtained is Metal/grapheme nanocatalyst.
A preparation method for Metal/grapheme nanocatalyst, specifically comprises the following steps:
(1) 10ml ~ 20ml is contained 10
-4mol/l, to the aqueous solution of the Graphene of the DMF solution of the organic negative hydrogen donor of saturated concentration and 5ml, 0.3mg/ml ~ 0.6mg/ml graphene oxide or chemical functionalization, stirs, then with ultrasonic wave process to limpid, obtain uniform dispersion liquid;
(2) 3ml ~ 4ml, 10 is added in the dispersion liquid obtained to step (1)
-4mol/l ~ 10
-2the aqueous solution of mol/l chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium, stirs, then obtains uniform dispersion liquid through ultrasonic process;
(3) in the dispersion liquid obtained to step (2), logical argon gas deoxygenation, uses this dispersion of ultraviolet-visible light illumination in argon gas atmosphere;
(4) in the dispersion after illumination, add extractant, the organic matter in system is fallen in extraction, by the pelleting centrifugation of lower floor's aqueous phase of obtaining and generation, wash with water, centrifugation again, by the solid drying obtained, obtains Metal/grapheme nanocatalyst.
Described graphene oxide can be obtained by other known methods, the invention provides a kind of preferred preparation method.
Described graphene oxide obtains through the following steps:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9 ~ 15ml concentrated sulfuric acid, is heated to 75 ~ 85 DEG C until potassium persulfate and phosphorus pentoxide all dissolve; Then add 1.8 ~ 2.2g graphite, at 75 ~ 85 DEG C of temperature, react 4 ~ 5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite obtained by step a joins in 75 ~ 85ml concentrated sulfuric acid of ice bath cooling, slowly adds 8 ~ 12g potassium permanganate under under magnetic stirring in this mixture, then at 30 ~ 40 DEG C, reacts 3 ~ 5h, reacts 1.5 ~ 2.5h again under room temperature; Slowly add the deionized water of 150 ~ 170ml, keep temperature to be no more than 50 DEG C, continue stirring 1.5 ~ 2.5h; Add water and the 30wt% hydrogen peroxide 8 ~ 12ml of 450 ~ 490ml again, produce jonquilleous solution, after this solution places 24h, outwell supernatant, then by remaining liquid, first wash twice respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator, and then wash twice with 10wt%HCl, last dialysis 6 ~ 8 days in water, the solid obtained is dry at 45 ~ 55 DEG C, obtained graphite oxide;
C. graphite oxide is peeled off as mono-layer graphite olefinic oxide
The graphite oxide that step b is obtained is placed in deionized water, and through ul-trasonic irradiation 10 ~ 30min, ultrasonic power is 150W, dissociates and obtains the graphene oxide solution of individual layer; Described graphite oxide: deionized water is 0.3mg ~ 0.6mg: 1mL.
The graphene oxide of described chemical functionalization is on Graphene, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain; Wherein, the structure of P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain is as follows:
1) P-TOLUENE SULFO ACID 99's base:
2) aziridinyl acetal chain:
Describedly on Graphene, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain can be obtained by other known methods, the invention provides a kind of preferred method.
Described P-TOLUENE SULFO ACID 99's base of modifying on Graphene is realized by following steps:
Get graphene oxide solution 40ml, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10, add the sodium borohydride of 100 ~ 200g wherein, under the condition of 80 ~ 90 DEG C, react 1 ~ 2h, then centrifugal, after the solid washed with water obtained twice, then be distributed in water the dispersion liquid making 0.3 ~ 0.6mg/l; Add the hydrochloric acid diazol 3 ~ 6ml containing 0.095M p-sulfonic acid benzene wherein, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, precipitation is after centrifugation, wash three times with the acetone/water mixed solvent that volume ratio is 3: 1 again, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
Described aziridinyl acetal chain of modifying on Graphene is realized by following steps:
Get graphene oxide solution 50ml; the 1-METHYLPYRROLIDONE adding 30 ~ 40ml (is called for short: NMP) ultrasonic 1h later; bubbling argon degasification 20min; [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols of 1 ~ 3g are added under argon shield condition; put into oil bath reaction 10 ~ 20h for 160 DEG C; after being cooled to room temperature; solid DMF is washed three times; wash six times with acetone, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
Further, described organic negative hydrogen donor is Isosorbide-5-Nitrae-dihydropyridine, 3,4-dihydropyrimidine-2-ketos or 2,3-dihydro-1H-benzimidazole.
Described Isosorbide-5-Nitrae-dihydropyridine is the compound with following structure:
Wherein R is H, Me, Et or 4-MeO-Ph.
Described 3,4-dihydropyrimidine-2-ketos are the compounds with following structure:
Wherein R
1=H, R
2=H; R
1=OMe, R
2=H; R
1=Me, R
2=H; R
1=Br, R
2=H; R
1=NO
2, R
2=H; R
1=OH, R
2=H or R
1=H, R
2=Cl.
Described 2,3-dihydro-1H-benzimidazoles are the compounds with following structure:
Further, described aqueous metallic ions is the aqueous solution of chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium.
Further, described illumination is ultraviolet-visible light illumination, carries out illumination with 500W high-pressure sodium lamp, wavelength X > 326nm, λ > 355nm or λ > 400nm.
Described deoxygenation leads to inert gas to system, as argon gas, and deoxygenation.
Further, described extractant is ethyl acetate, carrene, chloroform, benzene, toluene or ether.
A preparation method for Metal/grapheme nanocatalyst, comprises the following steps: 10 ~ 20ml contains 10
-4mol/l is to the aqueous solution of the saturated DMF solution of organic negative hydrogen donor and the Graphene of 5ml0.3 ~ 0.6mg/ml graphene oxide or chemical functionalization, stir 5 ~ 10min, then with ultrasonic wave process to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid; 3 ~ 4ml10 is added in dispersion liquid obtained above
-4~ 10
-2the aqueous solution of mol/l chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium, stir 5 ~ 10min, more ultrasonic process obtains uniform dispersion liquid, and logical argon gas deoxygenation, at argon gas atmosphere medium ultraviolet-this dispersion of visible ray illumination; Dispersion after illumination adds extraction into ethyl acetate and falls organic matter in system, and the pelleting centrifugation of lower floor's aqueous phase and generation, washes centrifugation again with water, and the solid obtained is dry in the baking oven of 50 DEG C, obtains Metal/grapheme nanocatalyst.
For solving above-mentioned 3rd technical problem, the invention provides the application of Metal/grapheme nanocatalyst; It can be used in organic synthesis and optical drive hydrogen production reaction, and catalytic performance is excellent.
The present invention has following beneficial effect:
1) preparation method's step of the present invention is simple, reaction condition is gentle, without the need to adding extra surfactant, can on Graphene load high degree of dispersion, undersized metal nanoparticle, especially adopt low-energy light can economize energy according to preparing Metal/grapheme nanocatalyst at short notice.
2) clean Metal/grapheme nanocatalyst only can need be separated by simple organic post processing, and can obtain the good catalyst solution of dispersion stabilization in DMF or water.
3) there is application prospect at optical graving in electrode of solar battery in the method for photochemistry Kaolinite Preparation of Catalyst.
4) the Metal/grapheme nanocatalyst catalytic performance prepared of the present invention is excellent, can be used in organic synthesis and optical drive hydrogen production reaction.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 with Isosorbide-5-Nitrae-dihydropyridine (R=H) for reducing agent, take graphene oxide as the transmission electron microscope picture of carrier, the platinum/graphene nano catalyst of preparation;
Fig. 2 be in embodiment 10 with Isosorbide-5-Nitrae-dihydropyridine (R=H) for reducing agent, be carrier through the Graphene that P-TOLUENE SULFO ACID 99 is functionalized, the transmission electron microscope picture of the platinum/graphene nano catalyst of preparation;
Fig. 3 be in embodiment 2 with Isosorbide-5-Nitrae-dihydropyridine (R=H) for reducing agent, take graphene oxide as carrier, the transmission electron microscope picture of the ruthenium/graphene nano catalyst of preparation;
Fig. 4 be in embodiment 3 with Isosorbide-5-Nitrae-dihydropyridine (R=H) for reducing agent, take graphene oxide as the transmission electron microscope picture of carrier, the palladium/graphene nano catalyst of preparation.
The product hydrogen kinetic curve of the optical drive hydrogen manufacturing system that is catalyst that Fig. 5 is the platinum/graphen compound prepared with embodiment 10.
Detailed description of the invention
Embodiment 1
A preparation method for Metal/grapheme nanocatalyst, comprises the following steps:
1, the synthesis of graphene oxide
A. the expansion process of graphite
The concentrated sulfuric acid of 9ml is heated to 80 DEG C, add 1.6g potassium persulfate and 1.6g phosphorus pentoxide, stir at this temperature and make solid entirely molten, then slowly add 2g, 320 object crystalline flake graphites, add in 5min, this mixed liquor reacts 4.5h at 80 DEG C, and reaction terminates cool to room temperature, then adds 350ml deionized water, after placing 12h, by the membrane filtration of this mixture through 0.2 μm, go the acid remained with a large amount of washings, solid at room temperature places 12h.
B. the oxidation of expanded graphite
The concentrated sulfuric acid getting 80ml is placed in the ice bath of 0 DEG C, the expanded graphite obtained by step a joins in sulfuric acid solution, then the potassium permanganate of 10g is under agitation slowly added, ensure in the process added that temperature is no more than 10 DEG C, at 35 DEG C, react 4h after adding, then react 2h again under room temperature, after reaction terminates, add 160ml deionized water in batches, originally can carry out under ice bath, ensure that temperature is no more than 50 DEG C; At room temperature 2h is reacted after water injection, and then add the water of 470ml, the hydrogenperoxide steam generator of 10ml, 30wt% is added again after adding, produce jonquilleous solution, after this solution places 24h, outwell supernatant, then by remaining centrifugal, first wash twice with 200ml containing the solution of 3wt% sulfuric acid, 1wt% hydrogen peroxide, and then wash twice with the 10wt%HCl of 200ml, the solids mixing of cleaning solution and graphite oxide all first will be stirred 30min by each washing, and then centrifugally removes cleaning solution; Obtain gel during last washing again with 200ml, now coagulant liquid is loaded in bag filter, in deionized water dialysis one week; Then the coagulant liquid after dialysis is poured in culture dish, and in the baking oven of 50 DEG C, dry 48h, obtains graphite oxide.
C. graphite oxide is peeled off as mono-layer graphite olefinic oxide
Be dispersed in water by graphite oxide, ultrasonic power is 150W, through ul-trasonic irradiation 20min, forms the dispersion liquid of 0.5mg/ml.
2, the synthesis of metal nanoparticles loaded Graphene
(1) 18ml is contained 1 of 20mg, the 5ml0.5mg/ml graphene oxide dispersion liquid that DMF solution and the step 1 of 4-dihydropyridine obtain mixes, stir 5min, then with ultrasonic wave process to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid;
(2) in dispersion liquid, 3ml, 10 is added
-3the aqueous solution of mol/l chloroplatinic acid, stir 5min, more ultrasonic process obtains uniform dispersion liquid, logical argon gas deoxygenation, λ > 400nm illumination 3h under 500W high-pressure sodium lamp adds optical filter;
(3) dispersion after illumination adds extraction into ethyl acetate and falls organic matter in system, the pelleting centrifugation of lower floor's aqueous phase and generation, wash centrifugation again with water, the solid obtained is dry in the baking oven of 50 DEG C, obtains Metal/grapheme nanocatalyst.
Embodiment 2
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.6mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 30mg, and it is 10 that step (2) adds concentration
-4the aqueous solution of the ruthenium trichloride of mol/l, illumination wavelength λ > 400nm, the illumination reaction time is 3h.
Embodiment 3
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 30mg, and it is 10 that step (2) adds concentration
-3the aqueous solution of the chlorine palladium acid sodium of mol/l, illumination wavelength λ > 400nm, the illumination reaction time is 3h.
Embodiment 4
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.3mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 20mg, and in step (2), the concentration of the aqueous solution of chloroplatinic acid is 10
-4mol/l, illumination wavelength λ > 355nm, the illumination reaction time is 3h.
Embodiment 5
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 25mg, and adding concentration in step (2) is 10
-2the aqueous solution of the ruthenium trichloride of mol/l, illumination wavelength λ > 400nm, the illumination reaction time is 3h.
Embodiment 6
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; In the synthesis step (1) of metal nanoparticles loaded Graphene, add 20mg3,4-dihydropyrimidine-2-keto replaces Isosorbide-5-Nitrae-dihydropyridine, and adding concentration in step (2) is 10
-3the aqueous solution of the chlorine palladium acid sodium of mol/l, illumination wavelength λ > 355nm, the illumination reaction time is 3h.
Embodiment 7
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; In the synthesis step (1) of metal nanoparticles loaded Graphene, add 30mg3,4-dihydropyrimidine-2-keto replaces Isosorbide-5-Nitrae-dihydropyridine, and the concentration adding the aqueous solution of chloroplatinic acid in step (2) is 10
-3mol/l, illumination wavelength λ > 355nm, the illumination reaction time is 3h.
Embodiment 8
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; In the synthesis step (1) of metal nanoparticles loaded Graphene, add 20mg2,3-dihydro-1H-benzimidazole replaces Isosorbide-5-Nitrae-dihydropyridine, and step adds 10 in (2)
-4the aqueous solution of the ruthenium trichloride of mol/l, illumination wavelength λ > 326nm, the illumination reaction time is 3h.
Embodiment 9
Repeat embodiment 1, it is only without part: in the synthesis step c of graphene oxide, and the concentration of described graphene oxide is 0.5mg/ml; In the synthesis step (1) of metal nanoparticles loaded Graphene, add 30mg2,3-dihydro-1H-benzimidazole replaces Isosorbide-5-Nitrae-dihydropyridine, and in step (2), the concentration of the aqueous solution of chloroplatinic acid is 10
-3mol/l, illumination wavelength λ > 326nm, the illumination reaction time is 3h.
Embodiment 10
A preparation method for Metal/grapheme nanocatalyst, comprises the following steps:
1, the synthesis of graphene oxide
Repeat the synthesis step of graphene oxide in embodiment 1.
2, the Graphene of chemical functionalization---on Graphene, modify P-TOLUENE SULFO ACID 99's base
Get graphene oxide solution 40ml obtained above, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10.Add sodium borohydride 160mg, 80 DEG C of reaction 1h, reaction terminates rear centrifugal, solid washed with water twice, and then be distributed in water the dispersion liquid making 0.5mg/ml, then the hydrochloric acid diazol 3.6ml containing 0.095M p-sulfonic acid benzene is added, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, after precipitation and centrifugal separation, then wash three times with the acetone/water mixed solvent that volume ratio is 3: 1, the aqueous solution of the solid obtained again is dispersed into after drying in the baking oven of 50 DEG C (ultrasonic power is 150W) 0.5mg/ml.
3, the synthesis of metal nanoparticles loaded Graphene
(1) 14ml is contained 1 of 20mg, the dispersion liquid of the Graphene of 5ml, 0.5mg/ml chemical functionalization that DMF solution and the step 2 of 4-dihydropyridine obtain mixes, stir 8min, then with ultrasonic wave process to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid;
(2) 3.5ml, 10 is added in dispersion liquid
-3the aqueous solution of mol/l chloroplatinic acid, stir 5min, more ultrasonic process obtains uniform dispersion liquid, logical argon gas deoxygenation, λ > 400nm illumination 3h under high-pressure sodium lamp adds optical filter;
(3) dispersion after illumination adds extraction into ethyl acetate and falls organic matter in system, the pelleting centrifugation of lower floor's aqueous phase and generation, wash centrifugation again with water, the solid obtained is dry in the baking oven of 50 DEG C, obtains Metal/grapheme nanocatalyst.
Embodiment 11
Repeat embodiment 10, it is only without part: the synthesis of the Graphene of step 2 chemical functionalization is on Graphene, modify aziridinyl acetal chain, and synthesis step is as follows:
The graphene oxide solution 50ml obtained; add 35mlNMP (1-METHYLPYRROLIDONE); ultrasonic 1h; bubbling argon degasification 20min; 1.1g [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols are added under argon shield condition; 160 DEG C of oil bath reaction 18h; after being cooled to room temperature; solid DMF is washed three times and washes six times with acetone, the solid obtained again disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in the baking oven of 50 DEG C after drying.
Embodiment 12
Repeat embodiment 10, it is only without part: in step 2, the last dispersion liquid concentration formed is 0.5mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 20mg, and adding concentration in step (2) is 10
-4the aqueous solution of the ruthenium trichloride of mol/l, illumination wavelength λ > 400nm, the illumination reaction time is 3h.
Embodiment 13
Repeat embodiment 11, it is only without part: in step 2, the last dispersion liquid concentration formed is 0.6mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, Isosorbide-5-Nitrae-dihydropyridine is 30mg, and in step (2), the concentration of the aqueous solution of chloroplatinic acid is 10
-3mol/l, illumination wavelength λ > 400nm, the illumination reaction time is 3h.
Embodiment 14
Repeat embodiment 10, it is only without part: in step 2, the last dispersion liquid concentration formed is 0.5mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, 3,4-dihydropyrimidine-2-ketos are 20mg, and in step (2), the concentration of the aqueous solution of ruthenium trichloride is 10
-4mol/l, illumination wavelength λ > 355nm, the illumination reaction time is 3h.
Embodiment 15
Repeat embodiment 11, it is only without part: in step 2, the last dispersion liquid concentration formed is 0.5mg/ml; Described in the synthesis step (1) of metal nanoparticles loaded Graphene, 2,3-dihydro-1H-benzimidazoles are 20mg, and in step (2), the concentration of the aqueous solution of chlorine palladium acid sodium is 10
-4mol/l, illumination wavelength λ > 326nm, the illumination reaction time is 3h.
Embodiment 16
A preparation method for Metal/grapheme nanocatalyst, comprises the following steps:
1, the synthesis of graphene oxide
Repeat the synthesis step of graphene oxide in embodiment 1.
2, the P-TOLUENE SULFO ACID 99's base of synthesis-on graphene modified of the Graphene of chemical functionalization
Get graphene oxide solution 40ml obtained above, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10; Add sodium borohydride 100mg, 1h is reacted at 80 DEG C, reaction terminates rear centrifugal, solid washed with water twice, and then be distributed in water the dispersion liquid making 0.6mg/ml, then the hydrochloric acid diazol 4ml containing 0.095M p-sulfonic acid benzene is added, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, after precipitation and centrifugal separation, then wash three times with the acetone/water mixed solvent that volume ratio is 3: 1, the solid obtained again disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in the baking oven of 50 DEG C after drying.
3, the synthesis of metal nanoparticles loaded Graphene
(1) 14ml contains 1 of 20mg, the dispersion liquid of 5ml, 0.5mg/ml chemical functionalization Graphene that DMF solution and the step 2 of 4-dihydropyridine obtain mixes, stir 10min, then with ultrasonic wave process to limpid (ultrasonic power is 150W), obtain uniform dispersion liquid;
(2) 3.5ml, 10 is added in dispersion liquid
-3the aqueous solution of mol/l chloroplatinic acid, stir 5 ~ 10min, more ultrasonic process obtains uniform dispersion liquid, logical argon gas deoxygenation, λ > 400nm illumination 3h under high-pressure sodium lamp adds optical filter;
(3) dispersion after illumination adds extraction into ethyl acetate and falls organic matter in system, the pelleting centrifugation of lower floor's aqueous phase and generation, wash centrifugation again with water, the solid obtained is dry in the baking oven of 50 DEG C, obtains Metal/grapheme nanocatalyst.
Embodiment 17
A preparation method for Metal/grapheme nanocatalyst, comprises the following steps:
1, the synthesis of graphene oxide
Repeat the synthesis step of graphene oxide in embodiment 1.
Aziridinyl acetal chain on the synthesis-graphene modified of 2, chemical functionalization Graphene
Get graphene oxide solution 50ml obtained above; add 45mlNMP (1-METHYLPYRROLIDONE); ultrasonic 1h; bubbling argon degasification 20min; 3g [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols are added under argon shield condition; 160 DEG C of oil bath reaction 20h; after being cooled to room temperature; solid DMF is washed three times and washes six times with acetone, the solid obtained again disperses (ultrasonic power is 150W) to become the aqueous solution of 0.4mg/ml in the baking oven of 50 DEG C after drying.
3, the synthesis of metal nanoparticles loaded Graphene
Repeat the step in embodiment 16.
To with Isosorbide-5-Nitrae-dihydropyridine (R=H) for organic negative hydrogen donor, without chemical functionalization and metal nanoparticles loaded on the Graphene of chemical functionalization, the composite catalyst obtained carries out transmission electron microscope sign.
As can be seen from transmission electron microscope picture, adopt the method for photoreduction, without chemical functionalization and all can the undersized platinum of load and ruthenium nano particle equably on the graphenic surface of chemical functionalization, the size of the nano particle obtained is that 3 ~ 5nm is (as Fig. 1,2, shown in 3), and Pd nano particle is of a size of 6-10nm (as shown in Figure 4).
Lattice fringe clearly can be seen, wherein the spacing of corresponding Pt (111) crystal face of 0.23nm from the corresponding HRTEM picture (Fig. 1 and Fig. 2) of Pt.
The interplanar distance of 0.23nm is demonstrated, same corresponding Pd (111) crystal face from the corresponding HRTEM picture (Fig. 4) of Pd.
In the above-described embodiment, the load capacity of degree that graphene oxide is reduced and metal nanoparticle can be regulated and controled by changing the type of organic negative hydrogen donor, the consumption of organic negative hydrogen donor and reaction condition etc.
Embodiment 18
The palladium/graphene nano catalyst obtained with embodiment 3 is catalyst, and study its catalytic effect in suzuki coupling reaction, the structure of reaction system comprises the following steps:
(1) palladium/graphene nano catalyst ultrasonic disperse embodiment 3 obtained, to (ultrasonic power is 150W) in DMF, forms the dispersion liquid of 0.3mg/mL;
(2) in the round-bottomed flask of 50ml, 50mg is added to methoxyl group iodobenzene, 30mg phenyl boric acid and 83mg anhydrous Na
2cO
3, then add 8ml palladium/graphene dispersion liquid obtained above and 2ml water;
(3) logical argon gas deoxygenation 30min, with mouth of sealing with wax, react 1.5h at oil bath is 85 DEG C after, stops reaction;
(4) in reactant liquor, 15ml water is added, be extracted with ethyl acetate three times (each 30ml), upper organic phase is again with saturated common salt washing twice (each 20ml), finally use anhydrous sodium sulfate drying, the solid silicagel column obtained after being spin-dried for solvent is separated, eluent is benzinum, obtains p-methoxyphenyl benzene, and productive rate is 80%.
By catalysis suzuki coupling reaction, palladium can be found to load on Graphene, have efficient catalytic performance, the effect of this enhancing probably derives from the coupling of the larger specific area of Graphene and Graphene and Technique of Nano Pd.
Embodiment 19
The platinum/graphene nano catalyst obtained with embodiment 10 is catalyst, studies the catalytic effect that it reacts at solar hydrogen making.
Hydrogen manufacturing system is using eosin W or W S as sensitising agent, and using triethanolamine as electronics sacrificial body, using platinum as catalyst, the structure of reaction system comprises the following steps:
(1) platinum/graphene nano catalyst ultrasonic disperse embodiment 10 obtained, to (ultrasonic power is 150W) in water, forms the dispersion liquid of 0.1mg/ml;
(2) in the teat glass of 15ml, add the triethanolamine aqueous solution of the 6ml0.83M of pH=7.1, and then add the eosin W or W S of 9.3mg, and the catalyst dispersion of 0.1mg/ml that 4ml step (1) obtains, stir 5min.Contrast hydrogen manufacturing system is simultaneously: do not add platinum/graphen catalyst, other components are identical; Or add the chloroplatinic acid of a great deal of, thus original position produces the platinum nano catalyst protected by photosensitizer molecule, other components are all identical;
(3) logical nitrogen deoxygenation 30min, with mouth of sealing with wax, squeezes into interior mark methane 300 microlitre, then illumination under wavelength X > 450nm, detects hydrogen growing amount in time with the U.S. gas-chromatography (TCD is detector) in sky.
As can be seen from Figure 5, the catalyst that obtains of the present invention can hydrogen catalyzed generation effectively under the driving of solar energy; Compared with control experiment, can find that Graphene greatly strengthen the catalysis product hydrogen effect of platinum; This enhancement effect probably derives from the larger specific area of Graphene and electron transfer rate fast, thus has effectively mediated the electro transfer between sensitising agent and platinum.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (16)
1. a Metal/grapheme nanocatalyst, is characterized in that, comprises the graphene oxide of chemical functionalization and the metal nanoparticle of load on it;
The graphene oxide of described chemical functionalization is on graphene oxide, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain; Wherein, the structure of graphene oxide being modified P-TOLUENE SULFO ACID 99's base and aziridinyl acetal chain is as follows respectively:
1) P-TOLUENE SULFO ACID 99's base:
2) aziridinyl acetal chain:
2. a kind of Metal/grapheme nanocatalyst according to claim 1, is characterized in that, described P-TOLUENE SULFO ACID 99's base of modifying on graphene oxide is realized by following steps: get graphene oxide solution 40ml, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10, add the sodium borohydride of 100 ~ 200g wherein, under the condition of 80 ~ 90 DEG C, react 1 ~ 2h, then centrifugal, after the solid washed with water obtained twice, then be distributed in water the dispersion liquid making 0.3 ~ 0.6mg/l; Add the hydrochloric acid diazol 3 ~ 6ml containing 0.095M p-sulfonic acid benzene wherein, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, precipitation is after centrifugation, wash three times with the acetone/water mixed solvent that volume ratio is 3:1 again, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
3. a kind of Metal/grapheme nanocatalyst according to claim 1, it is characterized in that, described aziridinyl acetal chain of modifying on graphene oxide is realized by following steps: get graphene oxide solution 50ml, add the ultrasonic 1h of 1-METHYLPYRROLIDONE of 30 ~ 40ml, bubbling argon degasification 20min, [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols of 1 ~ 3g are added under argon shield condition, put into oil bath reaction 10 ~ 20h for 160 DEG C, after being cooled to room temperature, solid DMF is washed three times, six times are washed with acetone, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
4. a kind of Metal/grapheme nanocatalyst according to claim 1, is characterized in that, described metal nanoparticle is platinum, ruthenium or palladium.
5. the preparation method of a Metal/grapheme nanocatalyst, it is characterized in that, comprise the following steps: the graphene oxide of graphene oxide or chemical functionalization is mixed with the DMF solution containing organic negative hydrogen donor, add the aqueous solution of metal ion afterwards, deoxygenation, this system of illumination, adds extractant extraction organic matter, aqueous phase and pelleting centrifugation, the solid obtained is Metal/grapheme nanocatalyst;
Described organic negative hydrogen donor is Isosorbide-5-Nitrae-dihydropyridine, 3,4-dihydropyrimidine-2-ketos or 2,3-dihydro-1H-benzimidazole;
The graphene oxide of described chemical functionalization is on graphene oxide, modify P-TOLUENE SULFO ACID 99's base or aziridinyl acetal chain; Wherein, the structure of graphene oxide being modified P-TOLUENE SULFO ACID 99's base and aziridinyl acetal chain is as follows respectively:
1) P-TOLUENE SULFO ACID 99's base:
2) aziridinyl acetal chain:
6. the preparation method of a kind of Metal/grapheme nanocatalyst according to claim 5, is characterized in that, comprise the following steps:
(1) 10ml ~ 20ml is contained 10
-4mol/l, to the aqueous solution of the Graphene of the DMF solution of the organic negative hydrogen donor of saturated concentration and 5ml, 0.3mg/ml ~ 0.6mg/ml graphene oxide or chemical functionalization, stirs, then with ultrasonic wave process to limpid, obtain uniform dispersion liquid;
(2) 3ml ~ 4ml, 10 is added in the dispersion liquid obtained to step (1)
-4mol/l ~ 10
-2the aqueous solution of mol/l metal ion, stirs, then obtains uniform dispersion liquid through ultrasonic process;
(3) in the dispersion liquid obtained to step (2), logical argon gas deoxygenation, uses this dispersion of ultraviolet-visible light illumination in argon gas atmosphere;
(4) in the dispersion after illumination, add extractant, the organic matter in system is fallen in extraction, by lower floor's aqueous phase of obtaining and pelleting centrifugation, washes with water, then centrifugation, by the solid drying obtained, obtains Metal/grapheme nanocatalyst.
7. the preparation method of a kind of Metal/grapheme nanocatalyst according to claim 5, is characterized in that, described Isosorbide-5-Nitrae-dihydropyridine is the compound with following structure:
Wherein R is H, Me, Et or 4-MeO-Ph.
8. the preparation method of a kind of Metal/grapheme nanocatalyst according to claim 5, is characterized in that, described 3,4-dihydropyrimidine-2-ketos are the compounds with following structure:
Wherein R
1=H, R
2=H; R
1=OMe, R
2=H; R
1=Me, R
2=H; R
1=Br, R
2=H; R
1=NO
2, R
2=H; R
1=OH, R
2=H or R
1=H, R
2=Cl.
9. the preparation method of a kind of Metal/grapheme nanocatalyst according to claim 5, is characterized in that, described 2,3-dihydro-1H-benzimidazoles are the compounds with following structure:
10. the preparation method of a kind of Metal/grapheme nanocatalyst according to claim 5 or 6, is characterized in that, described aqueous metallic ions is the aqueous solution of chloroplatinic acid, ruthenium trichloride or chlorine palladium acid sodium.
The preparation method of 11. a kind of Metal/grapheme nanocatalysts according to claim 5 or 6, it is characterized in that, described illumination carries out illumination with 500W high-pressure sodium lamp, wavelength X >326nm, λ >355nm or λ >400nm.
The preparation method of 12. a kind of Metal/grapheme nanocatalysts according to claim 5 or 6, it is characterized in that, described extractant is ethyl acetate, carrene, chloroform, benzene, toluene or ether.
The preparation method of 13. a kind of Metal/grapheme nanocatalysts according to claim 5, it is characterized in that, described graphene oxide obtains through the following steps:
A. the expansion process of graphite
1.6g potassium persulfate and 1.6g phosphorus pentoxide are joined in 9 ~ 15ml concentrated sulfuric acid, is heated to 75 ~ 85 DEG C until potassium persulfate and phosphorus pentoxide all dissolve; Then add 1.8 ~ 2.2g graphite, at 75 ~ 85 DEG C of temperature, react 4 ~ 5h, filter, wash, obtain expanded graphite;
B. the oxidation of expanded graphite
The expanded graphite obtained by step a joins in 75 ~ 85ml concentrated sulfuric acid of ice bath cooling, slowly adds 8 ~ 12g potassium permanganate under under magnetic stirring in this mixture, then at 30 ~ 40 DEG C, reacts 3 ~ 5h, reacts 1.5 ~ 2.5h again under room temperature; Slowly add the deionized water of 150 ~ 170ml, keep temperature to be no more than 50 DEG C, continue stirring 1.5 ~ 2.5h; Add water and the 30wt% hydrogen peroxide 8 ~ 12ml of 450 ~ 490ml again, produce jonquilleous solution, after this solution places 24h, outwell supernatant, then by remaining liquid, first wash twice respectively with 3wt% sulfuric acid and 1wt% hydrogenperoxide steam generator, and then wash twice with 10wt%HCl, last dialysis 6 ~ 8 days in water, the solid obtained is dry at 45 ~ 55 DEG C, obtained graphite oxide;
C. graphite oxide is peeled off as mono-layer graphite olefinic oxide
The graphite oxide that step b is obtained is placed in deionized water, and through ul-trasonic irradiation 10 ~ 30min, ultrasonic power is 150W, dissociates and obtains the graphene oxide solution of individual layer; Described graphite oxide: deionized water is 0.3mg ~ 0.6mg:1ml.
The preparation method of 14. a kind of Metal/grapheme nanocatalysts according to claim 5, is characterized in that, described P-TOLUENE SULFO ACID 99's base of modifying on graphene oxide is realized by following steps: get graphene oxide solution 40ml, with the Na of 5wt%
2cO
3regulate pH to 9 ~ 10, add the sodium borohydride of 100 ~ 200g wherein, under the condition of 80 ~ 90 DEG C, react 1 ~ 2h, then centrifugal, after the solid washed with water obtained twice, then be distributed in water the dispersion liquid making 0.3 ~ 0.6mg/l; Add the hydrochloric acid diazol 3 ~ 6ml containing 0.095M p-sulfonic acid benzene wherein, 2h is reacted in ice bath, reaction terminates to add 150ml acetone in this solution backward, separate out precipitation, precipitation is after centrifugation, wash three times with the acetone/water mixed solvent that volume ratio is 3:1 again, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
The preparation method of 15. a kind of Metal/grapheme nanocatalysts according to claim 5, it is characterized in that, described aziridinyl acetal chain of modifying on graphene oxide is realized by following steps: get graphene oxide solution 50ml, add the ultrasonic 1h of 1-METHYLPYRROLIDONE of 30 ~ 40ml, bubbling argon degasification 20min, [(2-nitrine ethyoxyl)-2-ethyoxyl]-2 ethoxy ethanols of 1 ~ 3g are added under argon shield condition, put into oil bath reaction 10 ~ 20h for 160 DEG C, after being cooled to room temperature, solid DMF is washed three times, six times are washed with acetone, the solid obtained in the baking oven of 50 DEG C after drying again ultrasonic disperse become the aqueous solution of 0.3 ~ 0.6mg/ml.
The application of 16. a kind of Metal/grapheme nanocatalysts as claimed in claim 1, is characterized in that, Metal/grapheme nanocatalyst is used for organic synthesis and optical drive hydrogen manufacturing system.
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| CN103120938A (en) * | 2013-03-04 | 2013-05-29 | 北京化工大学常州先进材料研究院 | Preparation method of Pd/graphene nano electro-catalyst |
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| CN103977835B (en) * | 2014-06-06 | 2016-08-24 | 上海师范大学 | Sulfonated graphite thiazolinyl Ru (bpy)32+nanometer heterogeneous catalysis and preparation method thereof |
| CN104888853B (en) * | 2015-04-17 | 2017-03-08 | 郑州大学 | A kind of graphene-supported PVP stable nanometer Ru catalyst, preparation method and its usage |
| CN105954334B (en) * | 2016-05-04 | 2018-11-23 | 嘉兴学院 | A kind of molecular imprinting electrochemical sensor and its application for detecting diphenylamines |
| CN107986266A (en) * | 2016-10-24 | 2018-05-04 | 林逸樵 | A kind of device and method for producing graphene/nanometer metal oxide composite |
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