CN108187719A - A kind of C3N4-Mt-SO3H composite materials and its preparation and application - Google Patents
A kind of C3N4-Mt-SO3H composite materials and its preparation and application Download PDFInfo
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- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a kind of C3N4‑Mt‑SO3H composite materials and its preparation and application.The C3N4‑Mt‑SO3H composite materials are the intercalation carbonitrides between montmorillonite layer, and in montmorillonite surface grafting sulfonic acid group.C provided by the invention3N4‑Mt‑SO3The preparation method of H composite materials is of low cost, easy to operate, substantially pollution-free to environment.The present invention also provides the C3N4‑Mt‑SO3H composite materials hydrolyze Hydrogenation for the application in the reaction of sorbierite as catalyst in cellulose one kettle way, and the catalyst can catalyzing cellulose hydrolysis obtains glucose simultaneously and glucose hydrogenation is converted into the reaction of sorbierite, and catalyst reproducible utilization.
Description
(1) technical field
The present invention relates to one kind using lamellar clay as carrier, in its surface grafting sulfonic acid, interlayer intercalation carbonitride
C3N4-Mt-SO3The preparation of H composite materials and its application in cellulose hydrolysis Hydrogenation sorbierite reaction.
(2) background technology
At present, the energy needed for the world and the Organic Chemicals overwhelming majority are examined from coal, oil, natural gas from long-range
Consider, they are not the preferable resources that the mankind can rely on for a long time.As Future and the energy that the mankind can rely on for a long time, it
Must be rich reserves, it is reproducible, and also its utilization will not cause environmental pollution.Based on this principle, based on plant
Biomass resource by be human future ideal chose.Cellulose is that one kind most wide, that content is most are distributed in nature is more
Sugared biomass resource, hydrocellulose are a kind of important channels of cellulose trans-utilization in recent years, and hydrolysate is with Portugal
Reducing sugar based on grape sugar.Glucose as a kind of important presoma needs that dehydration, oxidation plus hydrogen etc. further occurs
Reaction is converted to the chemical products of the high added values such as furfural, sorbierite, alcohol fuel.
Cellulose is the chain macromolecule compound being combined by D-Glucose unit with β -1,4 glycosidic bonds.Due to fibre
There is abundant hydroxyl in the plain structure of dimension, these hydroxyls are easy to and the oxygen-containing group in intramolecular or adjacent cellulosic molecule
Hydrogen bond is formed between group.Intramolecular hydrogen bond hardens cellulose chain, limits being freely rotated for glucose unit, and intermolecular hydrogen
Key promotes many cellulosic molecules close to each other again, collectively forms the crystal structure of cellulose, exactly this crystal structure so that
The property quite stable of cellulose, not soluble in water and common organic solvents.The approach of cellulose trans-utilization is generally divided into two steps,
The first step:Cellulose is broken β-Isosorbide-5-Nitrae glycosidic bond by the catalytic action of catalyst, forms Soluble Monosaccharide (such as glucose, fructose
Deng), second step:Hydrolysate glucose is hydrogenated to sorbierite by precious metal catalyst.Shape is hydrolyzed about first step cellulose
Into the reaction of Soluble Monosaccharide, the hydrolysis of solid acid catalysis cellulose carrys out the hot spot and liquid of always one research in recent years
Acid catalysis cellulose hydrolysis is compared, and solid acid catalysis has recyclable characteristic, is conducive to protection to environment and follow-up
The processing of product can also reduce the corrosion to equipment.It is reacted about second step, other chemicals is obtained using most by glucose
Efficient oxygen reduction catalyst is precious metals pt etc., but the shortcomings that the price and easy in inactivation of Pt costlinesses, significantly limit its quotient
Industry application.Therefore, exploitation Pt alternative materials become a vital task of catalytic field research.
To sum up, if it is possible to which glucose and glucose hydrogenation turn can be obtained by catalyzing cellulose hydrolysis simultaneously by developing one kind
The reaction of sorbierite and recyclable catalyst are turned to, one-step method realizes cellulose to high valuable chemicals, for cellulose
Efficiently use and be of great significance.
(3) invention content
First purpose of the invention is to provide a kind of C3N4-Mt-SO3H composite materials, structural stability is good, the composite wood
Material can catalyzing cellulose hydrolysis obtains glucose simultaneously and glucose hydrogenation is converted into the reaction of sorbierite.
Second purpose of the invention be to provide it is a kind of it is of low cost, easy to operate, to environment substantially free of contamination C3N4-Mt-
SO3The preparation method of H composite materials.
Third purpose of the present invention is to provide the C3N4-Mt-SO3H composite materials are as catalyst in cellulose one kettle way
Hydrogenation is hydrolyzed for the application in the reaction of sorbierite, it can catalyzing cellulose hydrolysis obtains glucose simultaneously and glucose adds
Hydrogen is converted into the reaction of sorbierite, and catalyst reproducible utilization.
For achieving the above object, the technical solution adopted by the present invention is specific as follows:
The present invention provides a kind of C3N4-Mt-SO3H composite materials are the intercalation carbonitride (g- between montmorillonite layer
C3N4), and in montmorillonite surface grafting sulfonic acid group.
Invention further provides a kind of C3N4-Mt-SO3The preparation method of H composite materials, including:
(1) montmorillonite is added in deionized water, it is for use to obtain mixture after stirring evenly;
(2) carbon nitride precursor is added in the mixture of step (1), at 10~150 DEG C stir 0.5~12h into
Row exchange adsorption, is homogenized, and wherein carbon nitride precursor is cyanamide, dicyandiamide, melamine, urea, ethylenediamine, nitrine
The combination of one or more of sour ammonium, cyanuric chloride and cyanuric acid;
(3) moisture in the homogenate obtained by step (2) is removed, obtains solid;
(4) by the solid obtained by step (3) dry 5 at a temperature of 20~150 DEG C~for 24 hours;
(5) dried solid abrasive is placed in into powder in tube furnace, with the speed of 1~10 DEG C/min in nitrogen atmosphere
Rate is from room temperature to 300 DEG C~800 DEG C, 1~10h of constant temperature calcining, natural cooling after roasting, and obtained product is named as
C3N4- Mt composite materials;
(6) by step (5) obtained by C3N4- Mt composite materials are added in toluene, are stirred evenly, and are homogenized;
(7) compound containing mercapto functional group is added in into the homogenate of step (6) again, is stirred back at 50~150 DEG C
Stream 1~for 24 hours, room temperature is subsequently cooled to, obtains mixed solution;Wherein the compound containing mercapto functional group be selected from it is one of following or
Arbitrary several combination:3- mercaptopropyl trimethoxysilanes (MPTMS), 2,3- sodium dimercaptopropane sulfonate salt (DMPS), 3- sulfydryls
Propionic acid, 3-sulfydryl-1-propane sulfonic acid sodium, 3- mercaptobenzoic acids, 4- mercaptobenzoic acids, methyl thioglycolate;
(8) mixed solution for obtaining step (7) filters, and is washed with toluene, dry, and obtained product is named as C3N4-
Mt-SH composite materials;
(9) by C3N4- Mt-SH composite materials are added in the mixed solution containing hydrogen peroxide, water and methanol or hydrogen peroxide
In, 1-48h is stirred at 10-100 DEG C, is then filtered, is washed, dry 5 at 20~150 DEG C~for 24 hours, grind into powder after drying
Shape, obtained product are named as C3N4-Mt-SO3H composite materials.
In step (1) of the present invention, the mass ratio of montmorillonite and deionized water addition is 1:5~1:50.
In step (2) of the present invention, the preferred dicyandiamide of carbon nitride precursor.
In step (2) of the present invention, the amount of the substance of the carbon nitride precursor of addition is montmorillonite cation exchange capacity
(CEC) 0.5~20 times, preferably 1~10 times, most preferably 6 times.
In step (2) of the present invention, exchange adsorption temperature is preferably 60~100 DEG C, most preferably 100 DEG C;During exchange adsorption
Between preferably 2~6h, most preferably 4h.
In step (3) of the present invention, it is recommended to use rotate or be centrifuged off moisture.
In step (5) of the present invention, heating rate is preferably 1~5 DEG C/min, most preferably 2.5 DEG C/min;Calcination temperature is preferred
It is 400~600 DEG C, most preferably 550 DEG C;Roasting time is preferably 3-5h, most preferably 4h.
In step (7) of the present invention, the compound containing mercapto functional group is preferably 3- mercaptopropyl trimethoxysilanes.
In step (7) of the present invention, the addition of the compound containing mercapto functional group is with C3N4It is counted on the basis of the quality of-Mt
For 1~4mL/g, preferably 1.5~2.5mL/g, most preferably 2.25mL/g.
In step (7) of the present invention, it is preferably 100~120 DEG C to be stirred at reflux temperature, and the time is 2~6h.
In step (9) of the present invention, in the mixed solution containing hydrogen peroxide, water and methanol, volume ratio (hydrogen peroxide:Water:First
Alcohol) it is 8:1:1~1:1:1.
In step (9) of the present invention, whipping temp is preferably room temperature, and mixing time is preferably 12~for 24 hours.
The preferably described preparation method of the invention carries out in accordance with the following steps:
(1) montmorillonite is added in deionized water, the mass ratio of montmorillonite and deionized water addition is 1:5~1:50,
It is for use that mixture is obtained after stirring evenly;
(2) dicyandiamide is added in the mixture of step (1), 2~6h is stirred at 60~100 DEG C and swaps suction
It is attached, it is homogenized;The amount of the substance of the dicyandiamide added in is 6 times of montmorillonite cation exchange capacity.
(3) moisture in the homogenate obtained by step (2) is removed, obtains solid;
(4) by the solid obtained by step (3) dry 5 at a temperature of 20~150 DEG C~for 24 hours;
(5) dried solid abrasive is placed in into powder in tube furnace, with the speed of 1~5 DEG C/min in nitrogen atmosphere
Rate is from room temperature to 400~600 DEG C, 3~5h of constant temperature calcining, natural cooling after roasting, and obtained product is named as
C3N4- Mt composite materials;
(6) by step (5) obtained by C3N4- Mt composite materials are added in toluene, are stirred evenly, and are homogenized;
(7) 3- mercaptopropyl trimethoxysilanes are added in into the homogenate of step (6) again, are stirred at reflux at 100~120 DEG C
2~6h is subsequently cooled to room temperature, obtains mixed solution;The addition of 3- mercaptopropyl trimethoxysilanes is with C3N4The quality of-Mt
On the basis of be calculated as 2.25mL/g;
(8) mixed solution for obtaining step (7) filters, and is washed with toluene, dry, and obtained product is named as C3N4-
Mt-SH composite materials;
(9) by C3N4- Mt-SH composite materials are added in hydrogen peroxide, and 12-24h is stirred at room temperature, then filters, washing, and 20
Dry 5 at~150 DEG C~for 24 hours, it is ground into powder after dry, obtained product is named as C3N4-Mt-SO3H composite materials.
Commercial goods can be used in the hydrogen peroxide that the present invention uses, such as 30% hydrogen peroxide of mass percent concentration of SILVER REAGENT.
Invention further provides the C3N4-Mt-SO3H composite materials are hydrolyzed as catalyst in cellulose one kettle way
Hydrogenation is for the application in the reaction of sorbierite.The application is specially:
In the stainless steel automatic high pressure reaction kettle for having polytetrafluoroethyllining lining, cellulose, C are added in3N4-Mt-SO3H is compound
Material and deionized water, wherein cellulose and C3N4-Mt-SO3The mass ratio of H composite materials is 0.5:1~8:1, it stirs evenly;
After reaction kettle is sealed, with high-purity H2Air in (purity >=99.999%) replacement reaction kettle, is filled with high-purity H2To setting pressure
It is worth (0.1~5MPa);Reaction kettle agitating and heating until set temperature (100 DEG C~400 DEG C) starts timing afterwards, reaches the anti-of setting
After between seasonable (1h~12h), ice-water bath cooling stops reaction, and gas is released in slowly decompression, and product centrifuges.Product liquid is used
Gas chromatograph-mass spectrometer (GC-MS) qualitative analysis, then with high performance liquid chromatography (HPLC) quantitative analysis, solid residue is then
It pours into beaker and is weighed after fully drying to calculate conversion ratio, dried solid residue can be as absorption organic dyestuff
Adsorbent.
In application of the present invention, cellulose is mainly microcrystalline cellulose.
In application of the present invention, cellulose and C3N4-Mt-SO3The mass ratio of H composite materials is preferably 4:1.
In application of the present invention, H2The preferred 4MPa of pressure, preferably 200 DEG C of reaction temperature, the reaction time is preferably 4 small
When.
Compared with prior art, the beneficial effects of the present invention are:
(1) C described in3N4-Mt-SO3H composite materials remain the structure feature of carbonitride and montmorillonite, and carbonitride and
Montmorillonite structure after 600 DEG C of high-temperature roastings is still constant, therefore the C3N4-Mt-SO3H composite structures stability is good;
(2) C described in3N4-Mt-SO3The raw material that H composite materials use in preparation are cheap and easy to get, and preparation method has
The advantages that reaction condition is relatively easy to control, is easy to operate and safe, the sample size of preparation are suitable for mass producing greatly;
(3) C described in3N4-Mt-SO3Traditional two-step method cellulose hydrolysis hydrogenation technique is integrated into one by H composite materials
Footwork realizes effective conversion of the cellulose to sorbierite.
(4) it illustrates
Fig. 1 is C3N4-Mt-SO3The preparation process schematic diagram of H composite materials;
Fig. 2 is Mt, C3N4,C3N4-Mt,C3N4-Mt-SO3The XRD spectra of H;
Fig. 3 is Mt, C3N4,C3N4-Mt,C3N4-Mt-SO3The infrared spectrum of H.
(5) specific embodiment
For a more detailed description to the present invention with embodiment below, these embodiments are only to the best embodiment party of the present invention
The description of formula, does not have any restrictions to protection scope of the present invention.
Embodiment 1
It weighs 5g montmorillonites (cation exchange capacity of montmorillonite used i.e. CEC is 50mmol/100g) and is placed in round bottom burning
In bottle, 50mL deionized waters are poured into, 20min is stirred, adds 0.42g dicyandiamides (2CEC), 4h is stirred at 100 DEG C and is handed over
Absorption is changed, then by product rotary evaporation to moisture completely without solid being put into evaporating dish later, 100 in thermostatic drying chamber
It DEG C is dried, dried solid abrasive is into pouring into quartz cell, then quartz cell is put into single tube tube furnace after powdered
In quartz socket tube, and sample is made to be in flat-temperature zone.Lead to nitrogen 1h after being sealed, remove the air in quartz socket tube.Tube furnace with
Temperature is risen to 550 DEG C, constant temperature 4h by the rate of 2.5 DEG C/min from room temperature, and natural cooling after roasting obtains product C3N4-
Mt composite materials.2gC is weighed again3N4- Mt is placed in round-bottomed flask, adds in 40mL toluene, 3mL 3- mercaptopropyl trimethoxysilanes
(MPTMS), it is stirred at reflux 4h for 110 DEG C, after cooled to room temperature, filtering, multiple, the removing sample surfaces that washs filtering with toluene
Extra MPTMS, dry 12h in 80 DEG C of baking ovens.Weigh the C after 1g drying3N4- Mt-SH samples are added to 30% (quality of 20mL
Percent concentration) in hydrogen peroxide, 12h is stirred at room temperature, by C3N4- Mt-SH is oxidized to C3N4-Mt-SO3Then H is filtered, washing,
Dry 12h, is ground into powder after dry at 100 DEG C.The catalyst prepared under this synthesis condition is denoted as sample 1.Sample 1
XRD spectra (Fig. 2), IR spectrograms (Fig. 3) are as follows.
XRD spectra shows C3N4-Mt-SO3H remains the characteristic peak of montmorillonite substantially, but the remitted its fury of characteristic peak
, illustrate C3N4-Mt-SO3H has the layer structure of montmorillonite.Compared with carbonitride, C3N4-Mt-SO3H is there are one 27.35 °
Faint peak, and the characteristic peak of 13 ° or so 100 crystal faces for not having a carbonitride, this result are not as not forming nitridation
Carbon, but since the amount of the carbonitride of formation is fewer.Because the presoma of carbonitride can form trimerization during polymerization
Cyanamide, melamine distil at 335 DEG C or so, so leading to the yield of carbonitride to reduce.C3N4-Mt-SO3H composite woods
Whether carbonitride is formed in material, we will continue through IR Characterization means to verify.Infrared spectrum shows C3N4-Mt-SO3H exists
806cm-1,1100cm-1,1240cm-1There is-SO at place3The characteristic absorption peak of H illustrates that sulfonic acid group is grafted to montmorillonite surface,
1240-1640cm-1The characteristic absorption peak at place corresponds to the skeleton vibrations of 3-S- triazine rings in carbonitride structural unit, shows carbonitride
It is intercalation between montmorillonite layer.
Embodiment 2
The quality of dicyandiamide in embodiment 1 is become into 0.84g (4CEC), other steps such as embodiment 1, under this synthesis condition
The catalyst of preparation is denoted as sample 2.
Embodiment 3
The quality of dicyandiamide in embodiment 1 is become into 1.26g (6CEC), other steps such as embodiment 1, under this synthesis condition
The catalyst of preparation is denoted as sample 3.
Embodiment 4
The quality of dicyandiamide in embodiment 1 is become into 1.68g (8CEC), other steps such as embodiment 1, under this synthesis condition
The catalyst of preparation is denoted as sample 4.
Embodiment 5
The quality of dicyandiamide in embodiment 1 is become into 2.10g (10CEC), other steps such as embodiment 1, this synthesis condition
The catalyst of lower preparation is denoted as sample 5.
Embodiment 6
By the quantitative change of 3- mercaptopropyl trimethoxysilanes (MPTMS) in embodiment 1 be 1.5mL, other steps such as embodiment
1, the catalyst prepared under this synthesis condition is denoted as sample 6.
Embodiment 7
By the quantitative change of 3- mercaptopropyl trimethoxysilanes (MPTMS) in embodiment 1 be 4.5mL, other steps such as embodiment
1, the catalyst prepared under this synthesis condition is denoted as sample 7.
Embodiment 8
By the quantitative change of 3- mercaptopropyl trimethoxysilanes (MPTMS) in embodiment 1 be 6.0mL, other steps such as embodiment
1, the catalyst prepared under this synthesis condition is denoted as sample 8.
Embodiment 9
20mL30% hydrogen peroxide in embodiment 1 is changed in the mixed solution of 20mL30% hydrogen peroxide, water, methanol, volume
Than (30% hydrogen peroxide:Water:Methanol=8:1:1), other steps such as embodiment 1, the catalyst prepared under this synthesis condition are denoted as
Sample 9.
Embodiment 10
Catalyst obtained by above-described embodiment 1~9 is applied in cellulose hydrolysis, hydrolysis property such as 1 institute of table
Show.
Cellulose hydrolysis hydrogenation reaction is carried out in the stainless steel automatic high pressure reaction kettle for having polytetrafluoroethyllining lining, often
Cellulose 1.00g, C are added in primary first-order equation3N4-Mt-SO3H catalyst 0.25g, deionized water 7mL, stir evenly;It will reaction
After kettle is sealed, with high-purity H2Air 3 times, is filled with high-purity H in (purity >=99.999%) replacement reaction kettle2To setup pressure value
4MPa.Reaction kettle agitating and heating, until start timing after 200 DEG C of set temperature, (4h), ice-water bath after the reaction time for reaching setting
Cooling stops reaction, and gas is released in slowly decompression, and product liquid is fitted into after centrifugation in reagent bottle and uses gas chromatography-mass spectrum
Combined instrument (GC-MS) qualitative analysis product, high performance liquid chromatography (HPLC) quantitative analysis product, solid residue are then poured into beaker
It weighs to calculate conversion ratio after fully drying.
Specific data such as following table:
Table 1.C3N4-Mt-SO3H catalyzing cellulose hydrolysis hydrogenation reaction cellulose conversion ratiosaAnd the yield of each productb
a:The matter of cellulose conversion ratio=(quality of the quality of unreacted cellulose-original fibers element)/original fibers element
Amount
b:Yield is calculated by peak area value in high performance liquid chromatography according to each product external standard method standard curve
Embodiment 10
By the quantitative change of 3- mercaptopropyl trimethoxysilanes (MPTMS) in embodiment 3 be 4.5mL, other same embodiments of step
3, the catalyst prepared under this synthesis condition is denoted as sample 9.Sample 9 is used for explore cellulose hydrolysis hydrogenation process conditions.First
Inquire into the yield of cellulose conversion ratio and each product under different hydrolysis hydroconversion conditions of sample 9.
Condition 1:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is:200 DEG C, 2h.
Condition 2:Catalyst is 0.50 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 2h.
Condition 3:Catalyst is 0.75 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 2h.
Condition 4:Catalyst is 1 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 2h.
Condition 5:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 160 DEG C, 2h.
Condition 6:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 180 DEG C, 2h.
Condition 7:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 220 DEG C, 2h.
Condition 8:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 240 DEG C, 2h.
Condition 9:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 1h.
Condition 10:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 4h.
Condition 11:Catalyst is 0.25 with cellulose mass ratio:1, hydrothermal reaction condition is 200 DEG C, 6h.
Specific data such as following table:
Cellulose conversion ratio under the different hydrolysis hydroconversion conditions of table 2.aAnd the yield of each productb
a:The matter of cellulose conversion ratio=(quality of the quality of unreacted cellulose-original fibers element)/original fibers element
Amount
b:Yield is calculated by peak area value in high performance liquid chromatography according to each product external standard method standard curve
It can be obtained by condition 1~4:With the increase of catalytic amount, there is no increase, phases for the yield of principal product glucose
The yield of anti-glucose can reduce.This is because one side glucose acidity of catalyst position and pyrohydrolysis from H+Effect
The lower further isomery of meeting, dehydration generation 5 hydroxymethyl furfural, 5 hydroxymethyl furfural can hydrolyze generation levulic acid.On the other hand
Cellulosic hydrolysates glucose is hydrogenated to sorbierite under the action of hydrogen position is added, and there are competitive relations for the two reactions.By
Condition 5~8,9~11 can obtain:With the raising of hydrolysis hydrogenation temperature, the extension of hydrogenation time, cellulose conversion ratio are hydrolyzed
Raising, hydrolysis principal product glucose yield increase always.Hydrolysis temperature increases, time lengthening, the H that liquid water dissociates+It can increase
It is more, H+Stronger B acid position is provided, hydrolysate glucose can be caused to continue dehydration generation 5 hydroxymethyl furfural, levulic acid etc.
By-product.Consider, in order to reduce the amount of by-product, product is facilitated to detach, optimum hydrolysising condition is:Catalyst and fiber
Plain mass ratio is 0.5:1, hydrothermal temperature is 200 DEG C, time 4h.
Claims (10)
1. a kind of C3N4-Mt-SO3H composite materials are the intercalation carbonitrides between montmorillonite layer, and in montmorillonite surface grafting sulphur
Acid groups.
2. a kind of C as described in claim 13N4-Mt-SO3The preparation method of H composite materials, including:
(1) montmorillonite is added in deionized water, it is for use to obtain mixture after stirring evenly;
(2) carbon nitride precursor is added in the mixture of step (1), 0.5~12h is stirred at 10~150 DEG C and is handed over
Absorption is changed, is homogenized, wherein carbon nitride precursor is cyanamide, dicyandiamide, melamine, urea, ethylenediamine, hydrazoic acid
The combination of one or more of ammonium, cyanuric chloride and cyanuric acid;
(3) moisture in the homogenate obtained by step (2) is removed, obtains solid;
(4) by the solid obtained by step (3) dry 5 at a temperature of 20~150 DEG C~for 24 hours;
(5) dried solid abrasive is placed in into powder in tube furnace, in nitrogen atmosphere with the rate of 1~10 DEG C/min from
Room temperature is to 300 DEG C~800 DEG C, 1~10h of constant temperature calcining, natural cooling after roasting, and obtained product is named as C3N4-
Mt composite materials;
(6) by step (5) obtained by C3N4- Mt composite materials are added in toluene, are stirred evenly, and are homogenized;
(7) compound containing mercapto functional group is added in into the homogenate of step (6) again, it is stirred at reflux 1 at 50~150 DEG C~
For 24 hours, room temperature is subsequently cooled to, obtains mixed solution;Wherein the compound containing mercapto functional group is selected from one of following or arbitrary
Several combinations:3- mercaptopropyl trimethoxysilanes, 2,3- sodium dimercaptopropane sulfonate salt, 3- mercaptopropionic acids, 3- sulfydryl -1- propane
Sodium sulfonate, 3- mercaptobenzoic acids, 4- mercaptobenzoic acids, methyl thioglycolate;
(8) mixed solution for obtaining step (7) filters, and is washed with toluene, dry, and obtained product is named as C3N4-Mt-SH
Composite material;
(9) by C3N4- Mt-SH composite materials are added in the mixed solution containing hydrogen peroxide, water and methanol or in hydrogen peroxide,
1-48h is stirred at 10-100 DEG C, is then filtered, is washed, dry 5 at 20~150 DEG C~for 24 hours, it is ground into powder, obtains after dry
To product be named as C3N4-Mt-SO3H composite materials.
3. preparation method as claimed in claim 2, it is characterised in that:Carbon nitride precursor is dicyandiamide.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that:In step (2), the carbon nitride precursor of addition
The amount of substance is 0.5~20 times of montmorillonite cation exchange capacity, preferably 1~10 times, most preferably 6 times.
5. preparation method as claimed in claim 2, it is characterised in that:In step (7), the compound containing mercapto functional group is
3- mercaptopropyl trimethoxysilanes.
6. the preparation method as described in claim 2 or 5, it is characterised in that:In step (7), the chemical combination containing mercapto functional group
The addition of object is with C3N41~4mL/g, preferably 1.5~2.5mL/g, most preferably 2.25mL/ are calculated as on the basis of the quality of-Mt
g。
7. preparation method as claimed in claim 2, it is characterised in that the preparation method carries out in accordance with the following steps:
(1) montmorillonite is added in deionized water, the mass ratio of montmorillonite and deionized water addition is 1:5~1:50, stirring
It is for use that mixture is obtained after uniformly;
(2) dicyandiamide is added in the mixture of step (1), 2~6h is stirred at 60~100 DEG C and swaps absorption, is obtained
To homogenate;The amount of the substance of the dicyandiamide added in is 6 times of montmorillonite cation exchange capacity.
(3) moisture in the homogenate obtained by step (2) is removed, obtains solid;
(4) by the solid obtained by step (3) dry 5 at a temperature of 20~150 DEG C~for 24 hours;
(5) dried solid abrasive is placed in into powder in tube furnace, in nitrogen atmosphere with the rate of 1~5 DEG C/min from
Room temperature is to 400~600 DEG C, 3~5h of constant temperature calcining, natural cooling after roasting, and obtained product is named as C3N4-Mt
Composite material;
(6) by step (5) obtained by C3N4- Mt composite materials are added in toluene, are stirred evenly, and are homogenized;
(7) 3- mercaptopropyl trimethoxysilanes are added in into the homogenate of step (6) again, it is stirred at reflux 2 at 100~120 DEG C~
6h is subsequently cooled to room temperature, obtains mixed solution;The addition of 3- mercaptopropyl trimethoxysilanes is with C3N4The quality of-Mt is base
Standard is calculated as 2.25mL/g;
(8) mixed solution for obtaining step (7) filters, and is washed with toluene, dry, and obtained product is named as C3N4-Mt-SH
Composite material;
(9) by C3N4- Mt-SH composite materials are added in hydrogen peroxide, and 12-24h is stirred at room temperature, then filters, washing, and 20~150
Dry 5 at DEG C~for 24 hours, it is ground into powder after dry, obtained product is named as C3N4-Mt-SO3H composite materials.
8. C as described in claim 13N4-Mt-SO3H composite materials hydrolyze Hydrogenation as catalyst in cellulose one kettle way
Application in the reaction of standby sorbierite.
9. application as claimed in claim 8, it is characterised in that:The application is specially:There is polytetrafluoroethyllining lining
In stainless steel automatic high pressure reaction kettle, cellulose, C are added in3N4-Mt-SO3H composite materials and deionized water, wherein cellulose with
C3N4-Mt-SO3The mass ratio of H composite materials is 0.5:1~8:1, it stirs evenly;After reaction kettle is sealed, with high-purity H2It puts
Air in reaction kettle is changed, is filled with high-purity H2To 0.1~5MPa of setup pressure value;Reaction kettle agitating and heating, until 100 DEG C~400 DEG C
After start timing, react 1h~12h, ice-water bath cooling stops reaction, and gas is released in slowly decompression, and product is centrifugally separating to obtain production
Product.
10. application as claimed in claim 9, it is characterised in that:Cellulose and C3N4-Mt-SO3The mass ratio of H composite materials is
4:1;Set H2Pressure value is 4MPa, and reaction temperature is 200 DEG C, and the reaction time is 4 hours.
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